TWI623423B - Laminated film - Google Patents

Abstract

The present invention relates to a laminated film, which is a laminated film having a surface layer on at least one side of a supporting substrate, and which satisfies the following conditions 1 to 3: condition 1: a condition of a maximum load of 0.5 mN and a holding time of 10 seconds The maximum displacement in the thickness direction of the surface layer in the load-unload test method using a micro hardness tester is 1.50 μm or more, and the residual displacement in the thickness direction of the surface layer is 1.30 μm or less; Condition 2: In rigidity The relative storage elastic modulus of the aforementioned surface layer at 100 ° C in the pendulum test method is higher than the relative storage elastic modulus of the aforementioned surface layer at 25 ° C; condition 3: the aforementioned surface layer in the tensile test method is at The elongation at break at 150 ° C is more than 50%.

The present invention provides a laminated film capable of satisfying formability, self-healing property, design property, and high-speed deformation resistance.

Description

Laminated film

The present invention relates to a laminated film which is excellent in designability and high-speed deformation resistance in addition to both the mold followability and abrasion resistance required for a molding material.

In molding materials such as decorative molding, a surface hardening layer is provided to prevent abrasion during molding or abrasion during use of an article after molding. However, because the surface hardened layer has insufficient elongation to follow the molding, cracks may occur during the molding, or in extreme cases, the film may crack or the surface hardened layer may peel. Therefore, it is generally applied to form a surface hardened layer after forming, or to completely harden it by heating or irradiation with active rays, etc. after forming in a semi-hardened state. However, since the formed article is processed into a three-dimensional shape, it is extremely difficult to provide a surface hardness layer in post-processing. Moreover, when forming in a semi-hardened state, the mold may be stained depending on the forming conditions. Based on the above, abrasion-resistant materials that can follow the molding are highly anticipated. In particular, "self-healing materials" that can repair minor abrasions through deformation of their own elastic recovery range have attracted much attention.

In addition, among these self-healing materials, materials that can identify the repair process of abrasions can directly identify their functions, which can improve the "designability" as a molding material when used in exterior components. By the attention. As for the self-healing materials as described above, materials of Patent Documents 1 and 2 have been proposed.

Furthermore, from the viewpoint of preventing abrasion of the molding material, it is required that scratches are not scratched even when an instant load such as an impact is applied to the surface of the material. Hereinafter, such characteristics are referred to as high-speed deformation resistance. In the daily use of molding materials, scratches are scratched due to instantaneous loads such as collisions in various places, which not only impairs the quality, but also has poor protection functions as articles. In particular, the number of electronic devices operated by hand, such as smartphones, touch panels, keyboards, and televisions and air-conditioners, has recently increased, such as touching accessories such as rings or watches during use, or touching furniture during transportation. Or, if you encounter foreign matter when you put it in the pocket or purse of your clothes, there are problems such as scratching the surface of the material.

In response to such a problem, as a member having moldability and high-speed deformation resistance, Patent Document 3 proposes "a polycarbonate resin composition characterized by containing 98 to 40% by mass of an aromatic polycarbonate resin (A Components); and 2 to 60% by mass of a resin component including a liquid crystal polyester resin (component B) and a thermoplastic polyester resin (component C) having a terminal carboxyl amount of 1 to 50 eq / ton; components B and C The mass ratio is (B) / (C) = 98/2 ~ 33/67, and the aromatic polycarbonate resin (component A) forms a continuous phase, and the liquid crystal polyester resin (component B) forms a dispersed phase. The average particle diameter of the liquid crystal polyester resin dispersed particles whose ratio of the minor diameter is 1 or more and less than 3 is in the range of 0.4 to 5 μm. " In addition, Patent Document 4 proposes "a thermoplastic resin composition comprising 0.1 to 15 parts by mass of an aromatic (meth) acrylate containing 50% by mass or more based on 100 parts by mass of polycarbonate (A). Unit of polymer (B) and 60 to 5 to 70 parts by mass A polymer (C) having a methyl methacrylate unit of at least mass% and a mass average molecular weight of 5,000 to 20,000 ".

[Prior technical literature] [Patent Literature]

[Patent Document 1] International Publication No. 2011/136042

[Patent Document 2] Japanese Patent No. 3926461

[Patent Document 3] Japanese Patent No. 5226294

[Patent Document 4] Japanese Patent No. 5107163

The technologies of Patent Literature 1 and Patent Literature 2 proposed as the self-healing materials have been confirmed by the present inventors and the like. Although they have excellent self-healing properties, they have a problem of insufficient high-speed deformation resistance.

In addition, regarding the technologies of the aforementioned Patent Documents 3 and 4, the results confirmed by the present inventors have shown that the high-speed deformation resistance is excellent, but these materials do not show formability or self-healing properties. The technical combinations of the aforementioned Patent Documents 1 and 2 are technologies that cannot be achieved by combining high-speed deformation resistance with self-healing properties, formability, and designability.

The problem to be solved by the present invention is to provide a laminated film having both formability, self-healing property, design property and high-speed deformation resistance.

The present inventors have worked hard to solve the above-mentioned problems, and as a result of repeated studies, they have completed the following inventions. That is, the present invention is as follows.

A laminated film is a laminated film having a surface layer on at least one side of a supporting substrate. The laminated film satisfies the following conditions 1 to 3: Condition 1: Use a micrometer under the conditions of a maximum load of 0.5 mN and a retention time of 10 seconds. The maximum displacement in the thickness direction of the surface layer in the load-unload test method of the hardness tester is 1.50 μm or more, and the residual displacement in the thickness direction of the surface layer is 1.30 μm or less; Condition 2: In the rigid pendulum test method The relative storage elastic modulus of the aforementioned surface layer at 100 ° C is higher than the relative storage elastic modulus of the aforementioned surface layer at 25 ° C; Condition 3: The aforementioned surface layer in the tensile test method at 150 ° C Rupture elongation is more than 50%.

According to the present invention, a laminated film having both formability, self-healing property, design property, and high-speed deformation resistance can be obtained.

1‧‧‧thickness displacement h (μm)

2‧‧‧Load P (mN)

3‧‧‧Maximum displacement

4‧‧‧ latent displacement

5‧‧‧ Residual displacement

6‧‧‧ aggravating steps

7‧‧‧ keep steps

8‧‧‧Uninstall steps

9‧‧‧ dependent variable (%)

10‧‧‧Stress (MPa)

11‧‧‧ breaking elongation (%)

12‧‧‧ Cracking energy (MPa)

13‧‧‧stress-strain curve

14‧‧‧ surface layer

15‧‧‧ middle layer

16‧‧‧ support substrate

17‧‧‧Multi-layer sliding mold

18‧‧‧multi-layer slot die

19‧‧‧Single-layer slot die

Figure 1 shows the stress-displacement curve obtained by the load-unload test method.

Figure 2 shows the stress-strain curve obtained by the tensile test method.

Fig. 3 is a cross-sectional view showing the configuration when the laminated film has an intermediate layer.

FIG. 4 is a cross-sectional view showing an example of a method for forming a surface layer and an intermediate layer in the manufacture of a laminated film.

FIG. 5 is a cross-sectional view showing an example of a method for forming a surface layer and an intermediate layer in the manufacture of a laminated film.

FIG. 6 is a cross-sectional view showing an example of a method for forming a surface layer and an intermediate layer in the manufacture of a laminated film.

[Form of Implementing Invention]

Before describing the embodiment of the present invention, the problems of the conventional technology, that is, the part that has both formability, self-healing, design, and high-speed deformation resistance, will be discussed from the perspective of the inventor.

[Comparison between the present invention and the conventional technology]

First, the reason why the self-healing materials of the conventional technologies described in Patent Literature 1 and Patent Literature 2 cannot have both formability and high-speed deformation resistance is because the conventional technology softens the coating film and increases the A large amount of deformability is used to exhibit moldability. Therefore, when a high-speed deformation load is applied, the amount of deformation of the coating film becomes too large, and the material is damaged due to peeling at the interface between the coating film and the substrate, and the high-speed deformation resistance is insufficient. To. Moreover, although it has moldability under room temperature conditions, the moldability under high temperature conditions is insufficient.

In addition, the technologies of Patent Document 3 or Patent Document 4 exhibit high impact resistance because the crosslink density of the material surface is high and hard, but on the other hand, they do not exhibit self-healing properties and designability. Furthermore, even when the materials of Patent Documents 1 or 2 and the materials of Patent Documents 3 or 4 are combined, self-healing properties, moldability, and high-speed deformation resistance are still trade-offs and cannot be combined.

The present inventors have found that it is effective to make specific mechanical characteristics of the surface layer of the laminated film within a specific range as a method for solving the above-mentioned problems. Specifically, it is found that the surface layer completely satisfies the following conditions 1 To the condition 3, the above problem can be solved.

Condition 1: Under the conditions of a maximum load of 0.5 mN and a holding time of 10 seconds, the maximum displacement in the thickness direction of the aforementioned surface layer in the load-unload test method using a micro hardness tester is 1.50 μm or more, and the thickness of the aforementioned surface layer The amount of residual displacement in the direction is 1.30 μm or less.

Condition 2: The relative storage elastic modulus of the aforementioned surface layer at 100 ° C in the rigid pendulum test method is higher than the relative storage elastic modulus of the aforementioned surface layer at 25 ° C.

Condition 3: The elongation at break of the aforementioned surface layer at 150 ° C in a tensile test method is 50% or more.

The present inventors have focused on the viscoelastic behavior of the surface layer of the laminated film, and found that the displacement amount of the surface layer relative to the load and the displacement amount after the load is released become a specific combination. The improvement of the properties and resistance to high-speed deformation is effective.

Specifically, it was found that in the load-unload test method using a micro hardness tester, the maximum displacement in the thickness direction of the surface layer when a load is applied and the residual displacement after the load is released are observed so that these two parameters are at A specific range is preferable. The measurement by the load-unload test method was performed by using a dynamic ultra-micro hardness tester to press a diamond-shaped triangular pyramid indenter (angle between edges 115 °) from the surface layer side of the laminated film. From the relationship between the displacement amount 1 (μm) in the thickness direction and the load 2 (mN) obtained by the load-unload test method, a stress-displacement curve can be obtained. FIG. 1 shows an example of a stress-displacement curve obtained by a load-unload test method. First, a load is applied and the indenter is laminated to the surface (emphasis step 6). When a maximum load of 0.5 mN is reached, it is directly held for 10 seconds (holding step 7). then , Remove the load (unload step 8). At this time, the maximum displacement amount in the thickness direction after the load is applied and before the unloading is the maximum displacement amount 3, the displacement amount during the holding step 7 is the creep displacement amount 4, and the displacement amount after the full unloading is the residual displacement.量 5。 Volume 5. The detailed measurement method will be described later.

From the viewpoints of moldability, self-healing, and designability, the aforementioned maximum displacement in the thickness direction of the surface layer is 1.50 μm or more, preferably 1.80 μm or more, and particularly preferably 2.00 μm or more. The maximum displacement amount indicates the magnitude of the displacement amount under load. The larger the maximum displacement amount, the higher the formability, self-healing, and designability. From the viewpoint of formability and design, the larger the maximum displacement in the thickness direction of the surface layer is, the better, but the self-healing property is not complete when the thickness is too large, so the upper limit value is considered to be about 3.00 μm. On the other hand, when the maximum displacement in the thickness direction of the surface layer is less than 1.50 μm, the formability is reduced.

Similarly, from the viewpoints of formability, self-healing, and design, the amount of the residual displacement is 1.30 μm or less. The residual displacement is the residual displacement after unloading. The smaller the residual displacement is, the smaller the residual recovery is, that is, the higher the self-healing property. Based on the self-repairing viewpoint of the surface layer, the smaller the residual displacement is, the better, but generally, since the self-repairing material is plastically deformed, the lower limit of the residual displacement in this measurement method is about 0.20 μm. On the other hand, when the amount of residual displacement in the thickness direction of the surface layer is greater than 1.30 μm, identifiable flaws remain after the surface layer self-repairs, resulting in deterioration of the appearance.

Furthermore, the inventors have focused on the self-healing properties of the surface layer of the laminated film, and also focused on the temperature dependence of the viscoelastic behavior of the surface layer, and found that the storage elastic modulus at high temperature is higher than the storage elasticity at room temperature. Modular materials can improve self-healing.

As a result of analysis of the above-mentioned phenomenon by the present inventors, it was found that when a scratch occurs on the surface layer, there is a correlation between the residual stress caused by the displacement and the storage elastic modulus. That is, it can be known that if the storage elastic modulus of the surface layer increases, the elastic force inside the surface layer becomes a force for releasing the residual stress accompanying the scratch, and as a result, the scratch can be repaired.

When the use of this property is expected based on actual use conditions, the laminated film of the present invention is suitable as a molding material for smartphones, etc., and is caused by the release of various electronic devices such as smartphones from the surface of the casing. When heat causes the surface temperature to rise, the self-repairing material also interacts with it to increase the temperature, thereby repairing the abrasions generated at room temperature, so it is expected to improve self-repairability.

Specifically, as a mechanical characteristic, we will focus on the relative storage elastic modulus in the rigid pendulum test method, and the relative storage elastic modulus of the surface layer at 100 ° C needs to be higher than the relative storage elastic modulus of the surface layer at 25 ° C. Store elastic modulus. The detailed measurement method will be described later.

From the viewpoint of formability, the tensile elongation of the surface layer at 150 ° C. in the tensile test method is 50% or more, preferably 80% or more, and more preferably 100% or more. The elongation at break indicates followability at the time of forming, and the larger the elongation at break indicates higher formability.

If the fracture elongation at 150 ° C is large, the above-mentioned laminated film can follow the shape of the formed article when it is formed under high temperature conditions, so that it can improve formability. The larger the fracture elongation at 150 ° C is, the better, but there is a difference in the softness between the surface layer and the support layer during molding, so the upper limit is considered to be about 300%. On the other hand, the elongation at break at 150 ° C is less than At 50%, the surface layer is cracked during the forming process, resulting in poor forming, and thus the formability is reduced.

Furthermore, from the standpoint of self-healing property and formability, the laminated film preferably satisfies the following condition 4 and condition 5.

Condition 4: The breaking elongation at 25 ° C. of the surface layer in the tensile test method is 150% or more.

Condition 5: The elastic recovery rate of the aforementioned surface layer at 25 ° C. in the tensile test method at a deformation amount of 150% is 70% or more.

Here, in order to measure the surface layer by a tensile test method, the surface layer of the laminated film is peeled off from a supporting substrate as a measurement sample, and then a tensile test is performed using a tensile tester. In the tensile test method with a tensile speed of 50 mm / min and a measurement temperature of 25 ° C., the elongation at the time of breaking the test piece was taken as the elongation at break. In the tensile test method with a tensile speed of 50 mm / minute and a measurement temperature of 25 ° C., the sample was stretched to a strain amount of 150%, and then the tensile load on the sample was released. This was used as a tensile test method at a deformation amount of 150%. The marked distance was measured before the measurement, and it was set to Lmm as an initial sample length, and the elastic recovery rate z% was calculated from the following formula.

Elastic recovery rate: z = (1- (L-50) / 100) × 100

The tensile test method and the detailed measurement method of elastic recovery rate are mentioned later. FIG. 2 shows an example of a stress-strain curve obtained by a tensile test method. The stress-strain curve 13 is drawn with the x-axis as the strain variable 9 (%) and the y-axis as the stress 10 (MPa). The breaking elongation 11 (%) and the oblique line portion 12 indicate the elongation and the breaking energy when the test piece is broken, respectively.

Based on self-healing and formability perspectives, in tensile tests The elongation at break of the aforementioned surface layer at 25 ° C in the method is preferably 150% or more, more preferably 180% or more, and even more preferably 200% or more. The elongation at break indicates the ultimate elongation at which the material is destroyed. The larger the elongation at break indicates the higher the damage resistance or formability of the material.

If the elongation at break is large, the damage of the surface layer can be suppressed when abrasion or deformation occurs during forming, and self-healing or formability can be improved. The larger the elongation at break, the better, but the self-repairing material has its limit due to the cross-connected road. The upper limit is considered to be about 500%. On the other hand, if the elongation at break is less than 150%, the surface layer is damaged during abrasion or deformation during molding, which reduces self-healing properties and moldability.

Examples of a method for making the surface elongation at break at 25 ° C. in the tensile test method 150% or more include a method of using a specific resin for the resin contained in the surface layer.

From the viewpoint of self-healing, the elastic recovery rate of the aforementioned surface layer at 25 ° C in the tensile test method at a deformation amount of 150% is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. . The elastic recovery rate indicates how much the surface layer size changes before and after the tensile test. The elastic recovery rate refers to how much the surface layer can recover to its original shape after deformation.

If the elastic recovery rate is high, when abrasion occurs or deformation occurs during molding, the material can be restored to recover the deformation, which can improve self-healing. The higher the elastic recovery rate, the better, with an upper limit of 100%. On the other hand, if the elastic recovery rate is less than 70%, when abrasion occurs or deformation occurs during molding, the deformation remains due to the failure to recover the material, and the self-healing property decreases.

As a method for making the elastic recovery rate of the surface layer at 25 ° C in the tensile test method at a deformation amount of 150% to 70% or more, a method of using a specific resin for the resin contained in the surface layer may be mentioned. .

In addition, the present inventors have paid attention to the stress-deformation behavior that occurs at the interface between the surface layer and the support substrate during molding or when a load such as an instant is applied. In particular, it was found that local adhesion failure occurs at the surface layer-supporting substrate interface under an instant load, and this is the reason for reducing the high-speed deformation resistance. Therefore, as a result of examining a method for preventing the surface layer-supporting substrate interface from being damaged at the interface, it is found that it is effective to select a supporting substrate having a surface with a certain degree of affinity with the solvent.

If the affinity between the surface of the support substrate and the solvent is high, when the surface layer is formed on the support substrate, since the components of the surface layer will penetrate the support substrate, the adhesion between the surface layer and the support substrate can be improved. This is effective for suppressing the local adhesive damage at the interface between the surface layer and the supporting substrate, and can improve the formability or resistance to high-speed deformation. Specifically, in the aforementioned laminated film, the supporting substrate preferably satisfies the following condition 6.

Condition 6: The swelling index of the support substrate is 0.01 or more.

The method for measuring the swelling index is described later.

The swelling index of the support substrate is preferably 0.01 or more, more preferably 0.05 or more, and even more preferably 0.10 or more. The swelling index indicates the affinity with the solvent and the coating composition. A larger swelling index indicates a higher adhesion between the supporting substrate and the surface layer, that is, a higher formability or high-speed deformation resistance.

If the swelling index of the supporting substrate is large, it can be improved The adhesion between the surface layer and the supporting substrate can improve formability or resistance to high-speed deformation. The larger the swelling index, the better, but if the swelling index is too large, the supporting substrate will be destroyed when the surface layer is formed, so the upper limit is considered to be about 10. On the other hand, if the swelling index is less than 0.01, the interface between the surface layer and the supporting substrate is destroyed during the deformation of the molding or when a load such as an impact is applied, resulting in a reduction in moldability or high-speed deformation resistance.

In order to make the support substrate have a swelling index of 0.01 or more, it can be achieved by selecting a support substrate having specific surface physical properties.

Furthermore, the present inventors paid attention to the mechanical characteristics under high-speed deformation conditions, and found that suppressing the plastic deformation of the surface layer is effective for improving the high-speed deformation resistance. Therefore, as a result of a discussion on a method for suppressing the plastic deformation of the surface layer, it was found that the stress-strain curve of the surface layer in the tensile test method preferably has specific conditions.

There are roughly two specific conditions. The first condition is that there is no yield point on the stress-strain curve. Since the yield point generally indicates the starting point of plastic deformation, if there is no yield point, the plastic deformation of the material can be prevented. 13 in FIG. 2 shows a stress-strain curve.

The second condition is that in a stress-strain curve in which the x-axis is a strain and the y-axis is a stress, the integrated area drawn by the x-axis and the curve has a value greater than or equal to a certain value. The integral area represents the energy required to break down the material per unit volume (hereinafter referred to as the fracture energy). 12 (slanted portion) in FIG. 2 indicates the breaking energy.

When the surface layer is plastically deformed, the amount of deformation does not depend on the stress, and the amount of deformation of the surface layer and the supporting base material varies. Due to the deviation of the amount of deformation, a slight difference in the surface layer-support substrate interface occurs. Since the fine adhesion is broken, the surface layer is destroyed due to the stress concentration starting from this, and as a result, the high-speed deformation resistance is reduced. On the other hand, since the above two conditions are effective in suppressing this destruction phenomenon, the high-speed deformation resistance can be improved.

Specifically, the laminated film preferably satisfies the following Condition 7 and Condition 8.

Condition 7: There is no yield point on the stress-strain curve of the aforementioned surface layer in the tensile test method.

Condition 8: The breaking energy per unit volume of the aforementioned surface layer in the tensile test method is 500 MPa or more.

The tensile test method and the method for measuring the breaking energy are described later.

From the viewpoint of high-speed deformation resistance, it is preferable that there is no yield point on the stress-strain curve of the aforementioned surface layer in the tensile test method. When there is no yield point on the stress-strain curve of the surface layer, when a load such as an instant is applied, the surface layer can be prevented from being damaged, and high-speed deformation resistance can be improved. On the other hand, when there is a yield point on the stress-strain curve, when a load such as an instant is applied, fine damage occurs on the surface layer, and the surface layer is damaged due to the stress concentration starting from it, resulting in high-speed deformation resistance. Sex decreased.

As a method of making a yield point not exist in the stress-strain curve of the said surface layer in the tensile test method, the method of using the specific resin for the resin contained in the said surface layer is mentioned.

From the viewpoint of high-speed deformation resistance, the breaking energy per unit volume of the aforementioned surface layer in the tensile test method is preferably 500 MPa or more, more preferably 750 MPa or more, and even more preferably 1,000 MPa or more. Split energy system It indicates the difficulty of material destruction, and the large fracture energy indicates the abrasion resistance or high-speed deformation resistance.

If the breaking energy is large, the surface layer can be prevented from being damaged when a load such as an instant is applied, and thus the high-speed deformation resistance can be improved. The larger the fracture energy system is, the better, but the self-healing material has its limit due to the cross-connected circuit. The upper limit is considered to be about 5,000 MPa. On the other hand, if the fracture energy is less than 500 MPa, the surface layer is destroyed when a load such as an instant is applied, resulting in a reduction in high-speed deformation resistance.

Examples of the method for making the fracture energy per unit volume of the surface layer in the tensile test method be 500 MPa or more include a method of using a specific resin for the resin contained in the surface layer.

Then, the present inventors paid attention to the polymer structure of the surface layer of the laminated film, and found that the amount of uncrosslinked components (hereinafter referred to as extractable components) in all the components contained in the surface layer is controlled. The improvement of formability is effective. The manifestation of self-healing in self-healing materials is due to the cross-linked components, but when a certain amount of extractable components exists, the softness of the surface layer can be improved. This is because the extractable component is free to move on the surface because it is not crosslinked. When a mechanical load is applied to the surface layer, voids are generated because the extractable component moves freely, and the deformable range is expanded by the movement of the crosslinked component to the void. As a result, the amount of deformation of the entire surface layer increases. Therefore, the flexibility of the surface layer is improved, and self-healing properties and moldability can be improved.

Specifically, the laminated film preferably satisfies the following condition 9 and condition 10.

Condition 9: The resin system contained in the surface layer includes the following (1) to (3).

(1) Polycarbonate segment

(2) Urethane bond

(3) Polysiloxane segment and / or polydimethylsiloxane segment of Chemical Formula 3

Condition 10: The amount of chloroform dissolved in the surface layer is 3% by mass or more and 20% by mass or less.

Here, the resin system includes a polymer to an oligomer. The method for measuring the amount of chloroform dissolved is described later.

(1) Polycarbonate segment refers to the segment shown in Chemical Formula 1; (2) Urethane bond refers to the bond shown in Chemical Formula 2; (3) Polysiloxane segment refers to Chemical Formula 3 The segment shown; the polydimethylsiloxane segment refers to the segment shown in Chemical Formula 4. These details are described later.

R ₁ is an alkylene group or a cycloalkylene group having a carbon number of 1 to 8, and n ₁ is an integer of 2 to 16.

R ₂ and R ₃ are each of OH and an alkyl group having 1 to 8 carbon atoms; the polysiloxane segment has at least one OH and alkyl group respectively; n ₂ is an integer of 100 to 300.

m ₁ is an integer from 10 to 300.

If the resin contained in the surface layer has (1) a polycarbonate segment, the self-healing property of the obtained surface layer can be improved, which is preferable.

If the resin contained in the aforementioned surface layer has (2) a urethane bond, the toughness of the obtained surface layer can be improved, and at the same time, the self-healing property is improved.

If the resin contained in the aforementioned surface layer has the polysiloxane segment (3) of the chemical formula 3 and / or polydimethylsiloxane segment, the heat resistance and weather resistance of the obtained surface layer can be improved, or the surface The abrasion resistance due to the lubricity of the layer is preferred.

In addition, one kind of resin contained in the surface layer may contain all the segments of the aforementioned (1) to (3), or a plurality of resins including any of the aforementioned segments of (1) to (3) may be contained in the surface layer.

From the viewpoints of self-healing property and formability, the amount of chloroform dissolved in the surface layer is preferably from 3% by mass to 20% by mass, more preferably from 4% by mass to 20% by mass, and even more preferably from 5% by mass to 20% by mass. the following.

If the amount of chloroform dissolved is large, the softness of the coating film can be improved by the aforementioned effects, and the self-healing property and moldability can be improved. On the other hand, when the dissolved amount of chloroform is too large, the toughness of the coating film decreases, so the upper limit consideration is preferably about 20% by mass. On the other hand, when the amount of chloroform dissolved is less than 3% by mass, the flexibility of the coating film is reduced, which leads to a decrease in self-healing properties and moldability.

Furthermore, the present invention etc. focuses on the layer structure of the laminated film, introduces an intermediate layer between the surface layer and the supporting substrate, and finds that the intermediate layer and the surface layer are connected to the supporting substrate in this order. It is effective in improving formability and resistance to high-speed deformation. A cross-sectional view of the laminated film in this form is shown in FIG. 3. That is, it is preferable that the intermediate layer 15 and the supporting base material 16 are laminated and grounded, and the surface layer 14 and the intermediate layer 15 are laminated and grounded.

Materials that exhibit self-healing properties through elastic recovery are used for the surface layer, and general thermoplastic resin is used for the laminated film that supports the substrate. Since the surface layer side becomes "entropy elastomer = rubber elastomer", the support substrate As an "energy elastic body", it can be said to be formed of materials that have greatly different thermal mechanical behavior. When such a film is heat-formed, the supporting substrate is plastically deformed and the deformation can be fixed, but the surface layer is deformed within the elastic deformation range. Therefore, the surface layer is in a state of being stretched by the elongation method with the support substrate, and residual stress is generated in the surface layer. Moreover, if it is subjected to further heating due to subsequent steps, such as injection molding, or high temperature in the use environment, the surface layer is an entropy elastomer, and the elastic modulus is higher than that during molding, and the elongation during molding is larger. When the breaking limit is reached, cracks occur.

Therefore, by introducing an intermediate layer having specific thermal characteristics and thickness, the residual stress generated in the aforementioned surface layer can be alleviated, and cracks in the surface layer can be suppressed even when there is a subsequent step or a load in the use environment, and It can suppress the damage at the coating film-substrate interface. As a result, self-healing property, formability, and high-speed deformation resistance can be improved.

Specifically, the following condition 11 is preferably satisfied.

Condition 11: The glass transition temperature of the intermediate layer is 60 ° C. or higher and 130 ° C. or lower.

Here, the condition 11 indicates a preferable range of the glass transition temperature of the intermediate layer, and more preferably 60 ° C or higher and 100 ° C or lower. If the glass transition temperature of the intermediate layer satisfies the above range, the residual stress between the surface layer-intermediate layer and the intermediate layer-supporting substrate can be relieved, and self-healing property or formability and high-speed deformation resistance can be improved. .

The glass transition temperature is a value obtained from a maximum value of temperature dispersion of a ratio (loss tangent) of a storage elastic modulus to a loss elastic modulus measured by a micro hardness tester. The details of the measurement method will be described later.

If the glass transition temperature of the intermediate layer is lower than 60 ° C, the adhesion between the surface layer, the intermediate layer, and the intermediate layer and the supporting substrate will be reduced, and there will be peeling at room temperature or scratches caused by rubbing of hard materials. situation. When the glass transition temperature of the intermediate layer is higher than 130 ° C., the conditions will vary, and cracks or peeling will easily occur during molding.

Furthermore, from the standpoint of self-healing or formability and resistance to high-speed deformation, the aforementioned intermediate layer preferably satisfies the following conditions 12:

Condition 12: The thickness of the intermediate layer is 0.1 μm or more and 5 μm or less.

Here, Condition 12 indicates a preferable range of the thickness of the intermediate layer, and more preferably 0.5 μm or more and 3 μm or less. If the thickness of the intermediate layer satisfies the above range, it is preferable to reduce the residual stress generated between the surface layer-intermediate layer and the intermediate layer-supporting substrate, and improve self-healing property or formability and high-speed deformation resistance.

If the thickness of the intermediate layer is thinner than 0.1 μm, the ability to absorb residual stress between the surface layer-intermediate layer and the intermediate layer-supporting substrate during molding will be slightly weakened; if it is thicker than 5 μm, the surface layer-intermediate layer and The adhesion between the intermediate layer and the supporting substrate will be slightly weakened.

The measurement of the storage elastic modulus, the loss elastic modulus, and the glass transition temperature of the intermediate layer will be described. These measurements can be performed using an ultra-micro hardness meter (Tribo Indenter manufactured by Hysitron Corporation) to obtain a modulus map image [storage elastic modulus (E ') image, loss elastic modulus (E ") image].

For example, the laminated film is embedded with an epoxy resin for an electron microscope (Quetol812 manufactured by Nisshin EM Co., Ltd.) and cured, and then the surface layer and An ultra-thin section of the cross section of the intermediate layer was used to prepare a measurement sample, and the measurement was performed under the following conditions. The elastic modulus was calculated using the Hertzian contact theory.

Measuring device: Tribo Indenter by Hysitron

Indenter: Diamond Cubecorner (curvature radius 50nm)

Measurement field of view: about 30mm square

Measurement frequency: 200Hz

Measurement environment: room temperature, in the atmosphere

Contact load: 0.3μN

Hereinafter, the measurement principle of the ultra-micro hardness tester will be described.

It is known that the stiffness (K) of the measurement system when the axisymmetric indenter is pressed into the sample is expressed by the formula (1).

Here, A is the projected area of the indentation that the sample and the indenter can contact, and E ^* is the composite elastic modulus of the indenter system and the sample system.

On the other hand, when the indenter is in contact with the surface of the sample, the front end of the indenter is regarded as a sphere, and the Hertzian contact theory related to the contact between a sphere and a semi-infinite plate is considered to be applicable. In Hertz's contact theory, the radius a of the indentation projection surface when the indenter is in contact with the sample is expressed by Equation (2).

Here, P is the load and R is the radius of curvature of the tip of the indenter.

Therefore, the projected area A of the indentation that can be contacted between the sample and the indenter is expressed by equation (3), and E ^* can be calculated by using equations (1) to (3).

Modulus mapping refers to the contact theory based on the above Hertz, which makes the indenter contact the surface of the sample, and makes the indenter slightly vibrate during the test. The method of obtaining the response amplitude and phase difference with respect to vibration as a function of time, and obtaining K (measurement of system stiffness) and D (sample vibration reduction).

When the vibration is a simple harmonic oscillator, the sum (detected load component) F (t) of the force of the indenter in the direction of the sample intrusion is expressed by the formula (4).

Here, the first term of formula (4) represents the force from the indenter shaft (m: mass of the indenter shaft), and the second term of formula (4) represents the force from the viscous component of the sample. (4) Item 3 represents the rigidity of the sample system, and t represents time. Since F (t) in equation (4) is time-dependent, it is expressed as in equation (5).

F ( t ) = F ₀ exp ( iωt ) (Equation 5)

Here, F ₀ is a constant and ω is an angular vibration number. Substituting equation (5) into equation (4) and equation (6), which is a special solution of ordinary differential equations, and then solving the equations, the relational expressions of equations (7) to (10) can be obtained.

herein, Is the phase difference. Since m is known at the time of measurement, the vibration amplitude (h ₀ ) and phase difference ( ) And excited vibration amplitude (F ₀ ), and K and D can be calculated from equations (7) to (10).

Consider E ^* as the storage elastic modulus (E ') aggregate formula (1) to formula (10), and use the Ks (= K-mω ² ) from the sample in the stiffness of the measurement system to calculate the storage from formula (11) Modulus of elasticity E '.

The loss elastic modulus can also be measured in the same manner as the aforementioned storage elastic modulus. Using the Ks from the sample in the stiffness of the measurement system in the aforementioned formula (8), the formula (11) is combined with the formula (11) ( 12) Calculate the loss elastic modulus E ”.

The glass transition temperature can also be measured in the same manner as the above-mentioned measurement of the storage elastic modulus. The loss tangent (tan δ) is obtained from the ratio of the storage elastic modulus and the loss elastic modulus calculated by the above method, and the obtained loss The peak temperature of tan (tan δ) was taken as the glass transition temperature (Tg).

Hereinafter, the laminated film of this invention is demonstrated in detail.

[Laminated film]

The laminated film of the present invention is a laminated film having a surface layer that satisfies the aforementioned conditions 1 to 3 on at least one side of a supporting substrate. The laminated film may be any of a film, a sheet, and a thin plate as long as it is planar. It is more preferable to have an intermediate layer between the support substrate and the surface layer.

In addition to the formability, design, self-healing, and high-speed deformation resistance of the subject of the present invention, the surface layer may also have gloss, fingerprint resistance, anti-reflection, anti-static, anti-fouling, electrical conductivity, hot wire Other functions such as reflection, near-infrared absorption, electromagnetic wave shielding, and easy adhesion.

The thickness of the surface layer is not particularly limited, but it is preferably 5 μm or more and 200 μm or less, and more preferably 10 μm or more and 100 μm or less. The thickness may be selected according to the other functions described above.

The thickness of the intermediate layer is not particularly limited, and it is preferably, for example, 0.1 μm or more and 5 μm or less, and more preferably 0.5 μm or more and 3 μm or less.

[Support substrate]

The resin constituting the supporting substrate may be any of a thermoplastic resin and a thermosetting resin. It may be a homopolymer, a copolymer, or a blend of two or more resins. More preferably, the resin constituting the supporting substrate is preferably a thermoplastic resin because of its good moldability.

As examples of the thermoplastic resin, polyolefin resins such as polyethylene, polypropylene, polystyrene, polymethylpentene, and the like; alicyclic polyolefin resins, polyamide resins such as nylon 6, nylon 66, and the like; aramide resins ; Polyester resin; polycarbonate resin; polyaromatic ester resin; polyacetal resin; polyphenylene sulfur resin; tetrafluoroethylene resin, trifluoroethylene resin, trifluorochloroethylene resin, tetrafluoroethylene-hexafluoropropylene copolymer, Fluorine resin such as vinylidene fluoride resin; acrylic resin; methacrylic resin; polyethylene glycol resin; polylactic acid resin, etc. The thermoplastic resin is preferably a resin having sufficient stretchability and followability. The thermoplastic resin is more preferably a polyester resin, a polycarbonate resin, an acrylic resin, or a methacrylic resin from the viewpoints of strength, heat resistance, and transparency.

Polyester resin refers to a general term of a polymer having an ester bond as a main chain of a main chain, and can be obtained by polycondensation of an acid component, an ester thereof, and a diol component. Specific examples include polyethylene terephthalate, polytrimethylene terephthalate, poly-2,6-naphthalene dicarboxylate, and polybutylene terephthalate. Moreover, it is also possible to copolymerize these with other dicarboxylic acid which is an acid component or a diol component, and its ester or a diol component. Among these, from the viewpoints of transparency, dimensional stability, heat resistance, and the like, polyethylene terephthalate or polyethylene-2,6-naphthalene dicarboxylate is particularly preferred.

In addition, various additives such as antioxidants, antistatic agents, crystal nucleating agents, inorganic particles, organic particles, viscosity reducing agents, heat stabilizers, lubricants, infrared absorbers, ultraviolet absorbers, and refraction can be added to the supporting substrate. Dopants used for rate adjustment. The supporting substrate may have any of a single-layer structure and a laminated structure.

The surface of the supporting substrate may be subjected to various surface treatments before the surface layer is formed. Examples of the surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, and ultraviolet light. Line irradiation treatment, high frequency treatment, glow discharge treatment, activated plasma treatment, laser treatment, mixed acid treatment and ozone oxidation treatment. Among these, a glow discharge treatment, an ultraviolet irradiation treatment, a corona discharge treatment, and a flame treatment are preferable, and a glow discharge treatment and an ultraviolet treatment are more preferable.

In addition, functional layers such as an easy-adhesion layer, an antistatic layer, an undercoat layer, and an ultraviolet absorbing layer may be provided in advance on the surface of the support substrate, separately from the surface layer and the intermediate layer. In particular, the easy-adhesion layer is provided good.

The supporting substrate is preferably a supporting substrate (hereinafter referred to as a supporting substrate A) having a swelling index of 0.01 or more as described above. If the supporting substrate A is used, the adhesion between the surface layer and the supporting substrate can be improved as described above. As a result, the formability or the high-speed deformation resistance can be improved, which is preferable.

As the supporting substrate A, products such as "COSMOSHINE" (registered trademark) A4300, A4100 (Toyobo Co., Ltd.), and "Panlite" (registered trademark) PC-2151 (Teijin Chemical Co., Ltd.) can be appropriately listed.

[Coating composition]

The method for producing the laminated film of the present invention is not particularly limited, and can be obtained through a step of applying a coating plastic on at least one side of the supporting substrate, a step of drying if necessary, and a step of curing.

This coating composition contains at least the aforementioned (1) polycarbonate segment, (2) urethane bond, (3) polysiloxane segment of Chemical Formula 3, and / or polydimethylsiloxane Resins in the alkane segment, or materials that can be formed during the coating process (hereinafter referred to as precursors). By using the coating composition in the manufacturing method described later, the resin contained in the surface layer can be used. With these segments and bonds. There are two types of coating compositions which are ideal for forming a surface layer.

The first type is a coating composition (hereinafter referred to as coating composition A) containing at least a urethane (meth) acrylate A and a siloxane compound. That is, the coating composition A is one in which a urethane (meth) acrylate A includes a polycarbonate segment and a urethane bond described later, and the siloxane compound includes a polysiloxane segment. Here, "(meth) acrylate" means an acrylate and / or a methacrylate. Coating composition A is a preferred coating composition when hardening by active energy rays is used in the hardening step of the coating process.

Next, the second type is a coating composition (hereinafter referred to as a coating composition B) containing at least a urethane (meth) acrylate B. That is, the coating composition B is a urethane (meth) acrylate B, which includes a polycarbonate segment, a urethane bond, and a polysiloxane segment of Chemical Formula 3 and / or a polydimethylsiloxane. Siloxane segment. The coating composition B is a preferable coating composition when the hardening step by the active energy ray is used in the hardening step of the coating process.

[Uranyl (meth) acrylates A, B]

As described above, the urethane (meth) acrylate A refers to a compound containing (1) a polycarbonate segment and (2) a urethane bond. In addition, the urethane (meth) acrylate B represents (1) a polycarbonate segment, (2) a urethane bond, and (3) a polysiloxane segment of Chemical Formula 3 and And / or a compound of a polydimethylsiloxane segment.

[Polycarbonate Segment]

The polycarbonate segment-containing resin preferably has at least one hydroxyl group (hydroxyl group). The hydroxyl group is preferably located at the end of a resin containing a polycarbonate segment.

As the polycarbonate segment-containing resin, polycarbonate diol is particularly preferred. Specifically, a polycarbonate diol represented by the chemical formula (5) is preferable.

R ₅ and R ₆ are an alkylene group or a cycloalkylene group having a carbon number of 1 to 8, and n ₃ is an integer of 2 to 16.

The number of repeats of the polycarbonate diol-based carbonate unit may be several, but when the number of repeats of the carbonate unit is too large, the strength of the hardened product of the urethane (meth) acrylate is reduced, so the repeat number is better It is 10 or less. The polycarbonate diol may be a mixture of two or more kinds of polycarbonate diols having different numbers of carbonate units.

The polycarbonate diol is preferably one having a number average molecular weight of 500 to 10,000, and more preferably 1,000 to 5,000. If the number average molecular weight is less than 500, it is difficult to obtain appropriate flexibility, and if the number average molecular weight is more than 10,000, heat resistance or solvent resistance may be reduced. Therefore, it is preferably the aforementioned level.

In addition, as the polycarbonate diol, UH-CARB, UD-CARB, UC-CARB (Ube Industrial Co., Ltd.), PLACCEL CD-PL, PLACCEL CD-H (DAICEL Chemical Industry Co., Ltd.) can be appropriately listed. , Kuraray Polyol C series (KURARAY Co., Ltd.), DURANOL series (Asahi Kasei Chemicals Co., Ltd.) and other products. These polycarbonate diols can be used alone or in combination of two or more.

The resin containing a polycarbonate segment may contain (or copolymerize) other segments or monomers in addition to the polycarbonate segment. For example, it may contain (or copolymerize) a compound containing a polysiloxane segment and / or a polydimethylsiloxane segment of the chemical formula 3 described below, and an isocyanate compound.

Preferably, the surface layer has (1) by reacting an isocyanate group-containing compound described later with a hydroxyl group of a polycarbonate diol to form a urethane (meth) acrylate and using it in a coating composition. ) Polycarbonate segments and (2) urethane bonds. As a result, the toughness of the surface layer can be improved, and at the same time, the self-healing ability is improved.

[Carbamate bond]

The coating composition for forming the surface layer can have a urethane bond by containing a commercially available urethane modified resin. In addition, when the surface layer is formed, a coating composition containing an isocyanate group-containing compound and a hydroxyl group-containing compound as a precursor can be applied to form a urethane bond in the coating step, and The surface layer contains a urethane bond.

Preferably, a urethane bond is formed by reacting an isocyanate group with a hydroxyl group, and the resin contained in the surface layer has a urethane bond. By reacting an isocyanate group with a hydroxyl group to form a urethane bond, the toughness of the surface layer can be improved, and at the same time, the self-healing property can be improved.

In addition, when the resin containing a polycarbonate segment, or the resin containing a polysiloxane segment and / or a polydimethylsiloxane segment of the chemical formula 3 described later has a hydroxyl group, it may be used by Heat and the like generate amino amines between these resins and the isocyanate group-containing compound as a precursor Citrate bond. If the surface layer is formed using a compound containing an isocyanate group and a resin having a polysiloxane group and / or a polydimethylsiloxane group having a chemical formula 3 having a hydroxyl group, the strength of the surface layer can be improved. Toughness and elastic recovery (self-healing) and surface smoothness are preferred.

The isocyanate group-containing compound refers to an isocyanate group-containing resin, or an isocyanate group-containing monomer or oligomer. Examples of the compound containing an isocyanate group include, for example, methylenebis-4-cyclohexyl isocyanate, trimethylolpropane adduct of methylenephenyl diisocyanate, and trimethylolpropane adduct of hexamethylene diisocyanate. Products, trimethylolpropane adduct of isophorone diisocyanate, isotricyanate body of methylenephenyl diisocyanate, isotricyanate body of hexamethylene diisocyanate, hexamethylene Polyisocyanates such as the biuret body of methyl diisocyanate, and block bodies of the isocyanate described above.

Among these isocyanate group-containing compounds, aliphatic isocyanates are better in self-healing properties than alicyclic or aromatic isocyanates. The isocyanate group-containing compound is more preferably a hexamethylene diisocyanate. From the viewpoint of heat resistance, the isocyanate group-containing compound is particularly preferably an isocyanate having an isotricyanate ring, and most preferably an isotricyanate body of hexamethylene diisocyanate. An isocyanate having an isotricyanate ring can form a surface layer having both self-healing properties and heat resistance properties.

[Siloxane compound]

The siloxane compound preferably contains a reactive site. The reactive site refers to a site that can react with other components by external energy such as heat or light. Examples of such reactive sites include alkane from the viewpoint of reactivity. Silyl groups, or carboxyl, hydroxyl, epoxy, vinyl, allyl, allyl, methacryl groups, etc., obtained by hydrolysis of oxysilyl and alkoxysilyl groups. Among these, from the viewpoints of reactivity and handleability, a vinyl group, an allyl group, an alkoxysilyl group, a silyl ether group or a silanol group, or an epoxy group, acrylfluorenyl group, and methacrylfluorenyl group are preferred.

When the coating composition contains a siloxane compound, the polysiloxane segment and / or the polydimethylsiloxane segment of Chemical Formula 3 is arranged on the outermost surface side of the surface layer of the laminated film of the present invention. Since the polysiloxane segment and / or the polydimethylsiloxane segment of the chemical formula 3 of the siloxane compound is arranged on the outermost surface side of the surface layer, it can be eliminated because it can improve the lubricity of the surface layer. The effect of the load can suppress the occurrence of irreparable scratches caused by the surface layer, thereby improving the self-healing property and high-speed deformation resistance of the surface layer, which is better.

[Polysiloxane segment]

In the present invention, the (poly) siloxane segment refers to a segment represented by the aforementioned Chemical Formula 3.

A partially hydrolyzed product of a hydrolyzable silane-containing silane compound, an organic silica sol, or a composition obtained by adding a hydrolyzable silane compound having a radical polymer to the organic silica sol can be used as the polymer having a polysiloxane chain. Use of paragraph compounds.

Examples of the compound having a polysiloxane segment include tetraalkoxysilane, methyltrialkoxysilane, dimethyldialkoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-methacryloxypropyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, etc. have hydrolysis Silicon A complete or partial hydrolyzate of an alkane compound or an organic silica sol dispersed in an organic solvent, or a hydrolyzed silane compound obtained by adding a hydrolyzable silane group to the surface of the organic silica sol.

In addition, the resin containing a polysiloxane segment may copolymerize other segments in addition to the polysiloxane segment. For example, a monomer component having a polycarbonate segment and a polydimethylsiloxane segment can be copolymerized.

As the resin containing a polysiloxane segment, it is preferred to copolymerize a monomer having a hydroxyl group capable of reacting with an isocyanate group, and the like. Copolymerization of a monomer containing a polysiloxane group with a monomer having a hydroxyl group capable of reacting with an isocyanate group can improve the toughness of the surface layer.

When the resin containing a polysiloxane segment is a copolymer having a hydroxyl group, if a coating material containing a resin (copolymer) containing a polysiloxane group having a hydroxyl group and an isocyanate group-containing compound is used, The composition is used to form a surface layer, and a surface layer having a polysiloxane segment and a urethane bond can be effectively formed.

[Polydimethylsiloxane segment]

As the compound having a polydimethylsiloxane segment, a copolymer in which a vinyl monomer is copolymerized with the polydimethylsiloxane segment is preferably used.

When the compound having a polydimethylsiloxane segment is a copolymer with a vinyl monomer, it may be any of a block copolymer, a graft copolymer, and a random copolymer. When a compound having a polydimethylsiloxane segment is a copolymer with a vinyl monomer, it is referred to as a polydimethylsiloxane-based copolymer.

A compound having a polydimethylsiloxane segment (polydimethylsiloxane copolymer) is a synthetic polydimethylsiloxane The segment copolymer can be produced by a living polymerization method, a polymer initiator method, a polymer chain moving method, etc. However, considering the productivity, it is better to use a polymer initiator method and a polymer chain moving method.

When the polymer initiator method is used, a compound having a polydimethylsiloxane segment (polydimethylsiloxane copolymer) can be polymerized by using a polymer azo radical represented by Chemical Formula 6 Initiator

(m ₂ is an integer of 10 to 300, and n ₄ is an integer of 1 to 50) It is obtained by copolymerizing with other vinyl monomers.

In addition, it is also possible to first synthesize a prepolymer in which a peroxy monomer and a polydimethylsiloxane having an unsaturated group are copolymerized at a low temperature to introduce a peroxide group into a side chain, and then perform the prepolymerization. Two-stage polymerization of polymer and vinyl monomer.

When the polymer chain transfer method is used, a compound having a polydimethylsiloxane segment (polydimethylsiloxane-based copolymer) can be obtained by, for example, using a silicone oil represented by Chemical Formula 7

(m ₃ is an integer of 10 to 300) After adding HS-CH ₂ COOH or HS-CH ₂ CH ₂ COOH to form a compound having an SH group, the chain movement of the SH group is used to make the polysiloxane and ethylene Based monomer copolymerization.

For a compound having a polydimethylsiloxane segment (polydimethylsiloxane-based copolymer), in order to synthesize a polydimethylsiloxane-based graft copolymer, for example, chemical formula 8 Compound shown

(m ₄ is an integer of 10 to 300), that is, a methacrylic acid ester of polydimethylsiloxane and the like are copolymerized with a vinyl monomer to be easily obtained.

Examples of the vinyl monomer used in the copolymer with a compound having a polydimethylsiloxane segment include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, and octyl acrylate. , Cyclohexyl acrylate, tetrahydrofuran acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, hard methacrylate Fatty ester, lauryl methacrylate, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, vinyl acetate, Vinyl chloride, vinylidene chloride, vinylidene fluoride, vinylidene fluoride, glycidyl acrylate, glycidyl methacrylate, Allyl glycidyl ether, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, maleic anhydride, acrylamide, methacrylamide, N-methylolpropene Amidine, N, N-Dimethacrylamidine, N, N-Dimethylaminoethyl Methacrylate, N, N-Diethylaminoethyl Methacrylate, Diacetone Acrylate Amine, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, allyl alcohol, and the like.

The polydimethylsiloxane copolymer is preferably an aromatic hydrocarbon solvent such as toluene or xylene, a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone, or ethyl acetate or butyl acetate. Ester-based solvents, alcohol-based solvents such as ethanol, isopropanol, and the like are produced by a solution polymerization method in a single or mixed solvent. If necessary, a polymerization initiator such as benzamidine peroxide and azobisisobutyronitrile may be used in combination. The polymerization reaction is preferably performed at 50 to 150 ° C for 3 to 12 hours.

The amount of the polydimethylsiloxane segment in the polydimethylsiloxane copolymer is based on the lubricity or stain resistance of the surface layer, and is the total component of the polydimethylsiloxane copolymer. Of 100% by mass, 1 to 30% by mass is preferred. The weight average molecular weight of the polydimethylsiloxane segment is preferably 1,000 to 30,000.

Regardless of the case where the polydimethylsiloxane segment is copolymerized or additionally added, the dimethylsiloxane is 100% by mass of the total components of the coating composition for forming the surface layer. If the chain segment is 1 to 20% by mass, it is also preferable from the viewpoints of self-healing, pollution resistance, weather resistance, and heat resistance. 100% by mass of the total components of the coating composition do not include a solvent that does not participate in the reaction, and include a monomer component that participates in the reaction.

When a resin containing a polydimethylsiloxane segment is used as a coating composition for forming a surface layer, it may contain (copolymerize) other segments in addition to the polydimethylsiloxane segment. . For example, it may contain (copolymerized) polycarbonate segments or polysiloxane segments.

In order to obtain a copolymer of a polycarbonate segment, a polydimethylsiloxane segment, and a polysiloxane segment suitable as the urethane acrylate A or the urethane acrylate B, In the synthesis of a polydimethylsiloxane-based copolymer, a method in which a polycarbonate segment and a polysiloxane segment are suitably added and copolymerized may be mentioned.

[Coating composition for intermediate layer]

The coating composition for the intermediate layer is a liquid which can form a material having a surface hardness higher than that of the surface layer by coating, drying, and curing on a supporting substrate, and contains a resin suitable for forming the intermediate layer, or a precursor thereof. .

The coating composition for the intermediate layer is not particularly limited, but preferably contains a thermosetting resin or an ultraviolet curing resin. It may be any of a thermosetting resin and an ultraviolet curing resin, and may be a mixture of two or more kinds.

The thermosetting resin preferably contains a hydroxyl group-containing resin and a polyisocyanate compound. Examples of the hydroxyl group-containing resin include an acrylic polyol, a polyether polyol, a polyester polyol, a polyolefin polyol, and a polyisocyanate compound. Carbonate polyols, urethane polyols, etc. may be one type or a mixture of two or more types. These acrylic polyols, polyether polyols, polyester polyols, polyolefin polyols, polycarbonate polyols, urethane polyols and the like are preferably those containing a hydroxyl group.

As long as the hydroxyl value of the hydroxyl-containing resin is between 1 and The range of 200 mgKOH / g is preferable from the viewpoints of durability, hydrolysis resistance, and adhesion when forming a coating film. When the hydroxyl value is less than 1, hardening of the coating film is hardly performed, and durability or strength is reduced. On the other hand, when the hydroxyl group is more than 200, the adhesiveness is reduced due to excessive curing shrinkage.

The acrylic polyol can be obtained, for example, by polymerizing acrylate or methacrylate as a component. Such an acrylic resin can be easily produced, for example, by copolymerizing (meth) acrylic acid, itaconic acid, maleic anhydride, and other monomers containing a carboxylic acid group using a (meth) acrylic acid ester as a component. Examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylic acid. Butyl ester, isobutyl (meth) acrylate, third butyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Cyclohexyl (meth) acrylate, methylhexyl (meth) acrylate, cyclododecyl (meth) acrylate, isoamyl (meth) acrylate, and the like. Examples of such acrylic polyols include DIC Corporation; (trade name "ACRYDIC" (registered trademark) series, etc.), Dacheng Fine Chemical Co., Ltd .; (trade name "Acrit" (registered trademark) series, etc.) , Japan Catalyst Co., Ltd. (trade name "Acryset" (registered trademark) series, etc.), Mitsui Chemicals Co., Ltd .; (trade name "TAKELAC" (registered trademark) UA series), etc., these products can be used.

Examples of the polyether polyol include polyethylene glycol or triol, polypropylene glycol or triol, polybutylene glycol or triol, polytetramethylene glycol or triol, and even these carbon numbers Addition polymers or block copolymers of dissimilar oxyalkylene compounds. As such polyether poly Examples of the alcohol include Asahi Glass Co., Ltd. (trade name "EXCENOL" (registered trademark) series, etc.), Mitsui Chemicals Co., Ltd .; (trade name "ACTCOL" (registered trademark) series, etc.), and these products can be used.

Examples of the polyester polyol include aliphatic diols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, decanediol, and cyclohexanedimethanol, and, for example, amber Aliphatic diprotic acids such as acids, adipic acid, sebacic acid, fumaric acid, suberic acid, azelaic acid, 1,10-decanedicarboxylic acid, cyclohexanedicarboxylic acid, etc. are used as the main raw material components. The aliphatic polyester polyol obtained by the reaction, or an aliphatic diprotic acid such as ethylene glycol, propylene glycol, butylene glycol, and aromatic diprotic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid. An aromatic polyester polyol obtained by reacting it as a main raw material component.

Examples of such polyester polyols include DIC Corporation; (trade name "POLYLITE" (registered trademark) series, etc.), KURARAY Corporation; (trade name "Kuraray Polyol" (registered trademark) series, etc.), Takeda Pharmaceutical Industry Co., Ltd .; (trade name "TAKELAC" (registered trademark) U series), these products can be used.

Polyolefin polyols are polymers and copolymers of 4 to 12 carbon diolefins such as butadiene or isoprene, diolefins of 4 to 12 carbons, and 2 to 12 carbons. The α-olefin copolymer of 22 contains a compound containing a hydroxyl group. The method for making it contain a hydroxyl group is not specifically limited, For example, the method of making a diene monomer react with hydrogen peroxide is mentioned. Furthermore, it can be converted into a saturated aliphatic by converting the remaining double bond into a hydrogen bond. Examples of such polyolefin-based polyols include Japan's Soda Co., Ltd .; (trade name "NISSO-PB" (registered trademark) G series, etc.) Idemitsu Kosan Co., Ltd .; (brand name "Poly bd" (registered trademark) series, "EPOL" (registered trademark) series, etc.), these products can be used.

As the polycarbonate polyol, for example, a polycarbonate polyol obtained by using only a dialkyl carbonate and 1,6-hexanediol can be used. However, from the viewpoint of lower crystallinity, it is used as a diol. Polycarbonate polyols obtained by copolymerizing 1,6-hexanediol, 1,4-butanediol, 1,5-pentanediol, or 1,4-cyclohexanedimethanol are preferred.

Examples of such polycarbonate polyols include Asahi Kasei Chemicals Co., Ltd., which is a copolymerized polycarbonate polyol; (trade names "T5650J", "T5652", "T4671", "T4672", etc.), Ube Kosan Co., Ltd. Ltd .; (trade name "ETERNACLL" (registered trademark) UM series, etc.), these products can be used.

The hydroxyl group-containing urethane polyol can be obtained, for example, by reacting a polyisocyanate compound with a compound containing at least two hydroxyl groups in one molecule, for example, by reacting the hydroxyl group with an excess ratio of isocyanate groups. Examples of the polyisocyanate compound used at this time include hexamethylene diisocyanate, toluene diisocyanate, m-xylene diisocyanate, isophorone diisocyanate, and the like. Examples of the compound containing at least two hydroxyl groups in one molecule include polyols, polyester diols, polyethylene glycols, polypropylene glycols, and polycarbonate diols.

The polyisocyanate compound used for the thermosetting resin refers to a resin containing an isocyanate group, or a monomer or oligomer containing an isocyanate group. Examples of the compound containing an isocyanate group include three of methylenebis-4-cyclohexyl isocyanate and methylenephenyl diisocyanate. Methylolpropane adduct, trimethylolpropane adduct of hexamethylene diisocyanate, trimethylolpropane adduct of isophorone diisocyanate, isocyanuric acid of methylphenyl diisocyanate Polyisocyanates such as acid ester bodies, isotricyanate bodies of hexamethylene diisocyanate, biuret bodies of hexamethylene isocyanate, and block bodies of the aforementioned isocyanates. Examples of polyisocyanate compounds used in such thermosetting resins include Mitsui Chemicals Co., Ltd .; (trade name "TAKENATE" (registered trademark) series, etc.), Japan Polyurethane Industrial Co., Ltd .; (trade name "CORONATE" (Registered trademark) series, Asahi Kasei Chemicals Co., Ltd .; (brand name "DURANATE" (registered trademark) series, etc.), DIC Corporation; (brand name "BURNOCK" (registered trademark) series, etc.), etc. can be used These products.

The ultraviolet-curable resin is not particularly limited, and preferred are polyfunctional acrylate monomers, oligomers, alkoxysilanes, alkoxysilane hydrolysates, alkoxysilane oligomers, and urethane acrylic acid. Ester oligomers and the like are more preferably polyfunctional acrylate monomers, oligomers, and urethane acrylate oligomers.

As an example of the polyfunctional acrylate monomer, a polyfunctional acrylate having two or more (meth) acryloxy groups in one molecule and a modified polymer thereof can be used, and as a specific example, neopentaerythritol tri (Meth) acrylate, neopentaerythritol tetra (meth) acrylate, dinepentaerythritol tri (meth) acrylate, dinepentaerythritol tetra (meth) acrylate, dinepentaerythritol Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, neopentaerythritol triacrylate hexamethylene diisocyanate aminomethyl Acid polymer, etc. These orders The body can be used singly or in combination of two or more kinds.

In addition, as the commercially available polyfunctional acrylic composition, Mitsubishi Rayon Co., Ltd .; (trade name "Diabeam" (registered trademark) series, etc.), Japan Synthetic Chemical Industry Co., Ltd .; (trade name "SHIKOH "(Registered trademark) series, etc.", Nagase Industry Co., Ltd .; (brand name "DENACOL" (registered trademark) series, etc.), Shin Nakamura Chemical Co., Ltd .; (brand name "NK ESTER" series, etc.), DIC Corporation Co., Ltd .; (trade name "UNIDIC" (registered trademark), etc.), East Asia Synthesis Co., Ltd .; ("ARONIX" (registered trademark) series, etc.), Nippon Oil Co., Ltd .; ("BLEMMER" (registered trademark) series, etc. ), Nippon Kayaku Co., Ltd .; (brand name "KAYARAD" (registered trademark) series, etc.), Kyoeisha Chemical Co., Ltd .; (brand name "LIGHTESTER" series, etc.), etc., these products can be used.

In order to impart the aforementioned characteristics, an acrylic polymer may be used. The acrylic polymer is more preferably unsaturated group-free, a weight average molecular weight of 5,000 to 200,000, and a glass transition temperature of 20 ° C to 200 ° C. When the glass transition temperature of the acrylic polymer is less than 20 ° C, the hardness decreases, and when it exceeds 200 ° C, the elongation is insufficient. A more preferable glass transition temperature ranges from 50 ° C to 150 ° C.

The acrylic polymer can impart hardness by having a hydrophilic functional group. Specifically, (meth) acrylic acid having a carboxyl group, itaconic acid, fumaric acid, maleic acid, etc., or 2-hydroxyethyl (meth) acrylate having a hydroxyl group, Unsaturated monomers having a hydrophilic functional group such as hydroxypropyl acrylate and the aforementioned unsaturated monomers Polymerization can introduce hydrophilic functional groups into acrylic polymers.

The weight average molecular weight of the acrylic polymer is preferably 5,000 to 200,000. When the weight average molecular weight is less than 5,000, hardness is insufficient; when the weight average molecular weight is more than 200,000, moldability including coating properties or toughness are insufficient. The weight average molecular weight can be adjusted by the blending amount of the polymerization catalyst and the chain-shifting agent, and the type of the solvent used.

The content ratio of the acrylic polymer is preferably 1% by mass or more and 50% by mass, and more preferably 5% by mass or more and 30% by mass of the total solid content of the coating composition for the intermediate layer. When it is 1% by mass or more, elongation can be significantly increased, and when it is 50% by mass or less, hardness can be maintained, which is preferable.

[Solvent]

The coating composition and the coating composition for an intermediate layer may contain a solvent. The number of solvents is preferably one or more and less than twenty, more preferably one or more and ten or less, even more preferably one or more and six or less, and particularly preferably one or more and four or less.

The "solvent" as used herein refers to a substance which is capable of evaporating approximately the entire amount during the drying step after coating and is liquid at normal temperature and pressure.

Here, the type of solvent is determined by the molecular structure of the solvent. That is, the same elemental composition, the same type and number of functional groups, but different bonding relationships (structural isomers), are not the aforementioned structural isomers, but no matter what configuration is given in the three-dimensional space Those who cannot properly overlap (stereoisomers) can be regarded as different kinds of solvents. For example, 2-propanol and n-propanol are considered as different solvents.

When plural solvents are included, the solvent with the lowest relative evaporation rate (ASTM D3539-87 (2004)) based on n-butyl acetate is used as the solvent B, and the relative evaporation rate of the solvent B is preferably 0.4. The following solvents.

Here, the relative evaporation rate of the solvent based on n-butyl acetate is the evaporation rate measured in accordance with ASTM D3539-87 (2004). Specifically, it is a value defined by the relative value of the evaporation rate based on the time required for 90% by mass of n-butyl acetate to evaporate under dry air.

When the relative evaporation rate of the solvent is greater than 0.4, the time required to align to the outermost surface of the surface layer of the polysiloxane segment and / or polydimethylsiloxane segment of the chemical formula 3 is shortened. Therefore, the self-healing property and high-speed deformation resistance of the obtained laminated film may decrease. The lower limit of the relative evaporation rate of the solvent B is not a problem as long as the solvent can be removed from the coating film by evaporation in the drying step, and it should be 0.005 or more in a general coating step.

Solvent B includes isobutyl ketone (relative evaporation rate: 0.2), isophorone (relative evaporation rate: 0.026), diethylene glycol monobutyl ether (relative evaporation rate: 0.004,), and diacetone alcohol (relatively Evaporation rate: 0.15), oleyl alcohol (relative evaporation rate: 0.003), ethylene glycol monoethyl ether acetate (relative evaporation rate: 0.2), nonylphenoxyethanol (relative evaporation rate: 0.25), propylene glycol monoethyl ether (relative evaporation rate) Evaporation rate: 0.1), cyclohexanone (relative evaporation rate: 0.32), and the like.

[Other ingredients in coating composition]

The coating composition for the surface layer and the coating composition for the intermediate layer The system preferably contains a polymerization initiator, a hardener, or a catalyst. The polymerization initiator and catalyst are used to promote the hardening of the surface layer. As the polymerization initiator, those who can initiate or promote the polymerization, condensation, or crosslinking of the components contained in the coating composition by anionic, cationic, or radical polymerization reactions are preferred.

Various types of polymerization initiators, hardeners, and catalysts can be used. Moreover, a polymerization initiator, a hardening agent, and a catalyst may be used individually, respectively, and you may use multiple polymerization initiator, a hardening agent, and a catalyst simultaneously. Furthermore, an acidic catalyst or a thermal polymerization initiator may be used in combination. Examples of the acidic catalyst include aqueous hydrochloric acid solution, formic acid, and acetic acid. Examples of the thermal polymerization initiator include a peroxide and an azo compound. Examples of the photopolymerization initiator include alkyl phenone-based compounds, sulfur-containing compounds, fluorenylphosphine oxide-based compounds, amine-based compounds, and the like. Examples of the crosslinking catalyst that can promote the formation of a urethane bond include dibutyltin dilaurate, dibutyl tin diethylhexoate, and the like.

The coating composition may further contain a melamine cross-linking agent such as alkoxymethylolmelamine, an acid-based cross-linking agent such as 3-methyl-hexahydrophthalic anhydride, and an amine-based cross-linking agent such as diethylaminopropylamine. Crosslinkers and other crosslinkers.

The photopolymerization initiator is preferably an alkyl phenone-based compound from the viewpoint of hardenability. Specific examples of the alkyl phenone-based compound include 1-hydroxy-cyclohexyl-phenyl-one, 2.2-dimethoxy-1.2-diphenylethane-1-one, and 2-methyl- 1- (4-methylthiophenyl) -2-N- Phenylpropane-1-one, 2-benzyl-2-dimethylamino-1- (4-phenyl) -1-butane, 2- (dimethylamino) -2-[(4- Tolyl) methyl] -1- (4-phenyl) -1-butane, 2-benzyl-2-dimethylamino-1- (4-N- Phenylphenyl) -1-butane, 2- (dimethylamino) -2-[(4-tolyl) methyl] -1- [4- (4-N- Phenyl) phenyl] -1-butane, 1-cyclohexyl-phenyl ketone, 2-methyl-1-phenylpropane-1-one, 1- [4- (2-ethoxy) -benzene Group] -2-hydroxy-2-methyl-1-propane-1-one, bis (2-phenyl-2-lanthoxyacetic acid) oxybisethylene, and those having a high molecular weight.

Moreover, as long as it is in the range which does not prevent the effect of this invention, a leveling agent, an ultraviolet absorber, a slip agent, an antistatic agent, etc. may be added to a coating composition. Thereby, the surface layer and the intermediate layer can contain a leveling agent, an ultraviolet absorber, a slip agent, an antistatic agent, and the like. Examples of the leveling agent include acrylic copolymers, polysiloxane-based, and fluorine-based leveling agents. Specific examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, aniline oxalate-based, And hindered amine UV absorbers. Examples of the antistatic agent include lithium salts, sodium salts, potassium salts, rubidium salts, cesium salts, magnesium salts, and calcium salts.

[Manufacturing method of laminated film]

The surface layer formed on the surface of the laminated film of the present invention is preferably formed by coating the aforementioned coating composition for a surface layer on the aforementioned supporting substrate, and drying and curing it. Hereinafter, the step of applying the coating composition is described as a coating step, the step of drying is described as a drying step, and the step of curing is described as a curing step. As for the coating composition for a surface layer, two or more coating compositions may be applied sequentially or simultaneously to form a surface layer including two or more layers.

In addition, when the laminated film of the present invention has an intermediate layer, the coating composition for the surface layer and the intermediate layer coating group are combined The finished product is coated on the above-mentioned supporting substrate successively or simultaneously, and dried and hardened to form it. As for the coating composition for an intermediate layer, two or more coating compositions may be applied sequentially or simultaneously to form an intermediate layer including two or more layers.

That is, in the aforementioned laminated film, it is preferable to satisfy the following condition 13 or condition 14.

Condition 13: The surface layer and / or the intermediate layer are formed by sequentially coating two or more coating compositions on a support substrate, and drying and hardening them.

Condition 14: The surface layer and / or the intermediate layer are formed by simultaneously coating two or more kinds of coating compositions on a supporting substrate, and drying and hardening them.

The "sequential coating" as referred to herein refers to the formation of a surface layer by coating one coating composition on a supporting substrate, drying and hardening it, and coating another coating composition thereon, and drying and hardening it. Or the meaning of the middle layer. By appropriately selecting the type of coating composition to be used, it is possible to control the magnitude or gradient of the elastic modulus of the entire surface layer (the surface layer and the intermediate layer are defined together as the entire surface layer)-the supporting substrate side. , Support the size of the elastic modulus of the substrate and the entire surface layer. Furthermore, by appropriately selecting the type, composition, drying conditions, and hardening conditions of the coating composition, the shape of the elastic modulus distribution in the entire surface layer can be controlled stepwise or continuously.

In addition, "simultaneous coating" means that in the coating step, two or more coating compositions are simultaneously coated on a supporting substrate, and then they are dried and hardened.

In the coating step, the method for coating the coating composition is not particularly limited, but it is preferred to apply the coating composition by a dip coating method, a roll coating method, a bar coating method, a gravure coating method, or a die coating method (U.S. Patent No. Instruction No. 2681294) and the like are applied to a supporting substrate. Furthermore, among these coating methods, a gravure coating method or a die coating method is more preferable as the coating method.

In addition, when two or more kinds of coating compositions are applied simultaneously, the method is not particularly limited, but methods such as multilayer sliding die coating, multilayer slit die coating, and wet-on-wet coating can be used.

An example of multilayer sliding die coating is shown in FIG. 4. In multilayer sliding die coating, a liquid film containing two or more types of coating composition is sequentially laminated using a multilayer sliding die 17 and then coated on a supporting substrate.

An example of multi-layer slit die coating is shown in FIG. 5. In multilayer slit die coating, a liquid film containing two or more coating compositions is applied to a support substrate using a multilayer slit die 18 and laminated at the same time.

An example of wet to wet coating is shown in FIG. 6. In wet-on-wet coating, a single-layer liquid film containing a coating composition discharged from a single-layer slit die 19 is formed on a supporting substrate, and the single-layer liquid A liquid film of another coating composition discharged from the layer slit die 19.

After the coating step, the liquid film coated on the supporting substrate is dried by a drying step. From the viewpoint of completely removing the solvent from the obtained laminated film, the drying step is preferably accompanied by heating of the liquid film.

Examples of the heating method in the drying step include thermal drying ( Close contact with hot objects), convection heat conduction (hot air), radiation heat conduction (infrared), other (microwave, induction heating) and other methods. Among them, it is also necessary to precisely make the drying speed uniform based on the width direction, and it is preferable to use a method of convection heat conduction or radiation heat conduction.

The drying process of the liquid film in the drying step can generally be divided into (A) a constant speed drying period and (B) a deceleration drying period. For the former, the diffusion of solvent molecules on the surface of the liquid film into the atmosphere becomes rate-controlling, so the drying rate is constant in this interval; the drying rate is determined by the partial pressure of the evaporated solvent in the atmosphere, Dominated by wind speed and temperature, the film surface temperature is a value determined by the temperature of the hot air and the partial pressure of the evaporated solvent in the atmosphere and is constant. In the latter case, because the diffusion of the solvent in the liquid film becomes a rate limit, the drying speed does not show a certain value in this interval and continues to decrease. Dominated by the diffusion coefficient of the solvent in the liquid film, the film surface temperature gradually increases. The drying speed referred to here refers to the amount of solvent evaporation per unit time and unit area, and is determined by g. m ^-2 ． Caused by s ^-1 .

The drying speed is preferably 0.1g. m ^-2 ． s ^-1 or more 10g. m ^-2 ． s ^-1 or less, more preferably 0.1g. m ^-2 ． s ^-1 or more 5g. m ^-2 ． s ^-1 or less. Keeping the drying speed in the constant-speed drying section in this range can prevent unevenness caused by uneven drying speed.

As long as a preferable drying speed is obtained, it is not particularly limited. In order to obtain the above drying speed, the temperature is preferably 15 ° C to 129 ° C, more preferably 50 ° C to 129 ° C, and particularly preferably 50 ° C to 99 ° C.

During the deceleration drying, the polysiloxane segment and / or the polydimethylsiloxane segment of Chemical Formula 3 are carried out together with the evaporation of the residual solvent. Alignment. In this process, since it takes time for alignment, the temperature increase rate of the film surface during deceleration and drying is preferably 5 ° C./second or less, and more preferably 1 ° C./second or less.

After the drying step, a hardening operation may be further performed by irradiating heat or active energy rays (hardening step).

In terms of active energy rays, from the viewpoint of general versatility, electron rays (EB rays) and / or ultraviolet rays (UV rays) are preferred. In the case of hardening by ultraviolet rays, from the viewpoint of preventing the obstruction of oxygen, the lower the oxygen concentration, the better, and more preferably the hardening under a nitrogen environment (nitrogen flushing). When the oxygen concentration is high, the hardening of the outermost surface is hindered, and the hardening of the surface is weakened, resulting in low self-healing properties and high-speed deformation resistance. Examples of the type of the ultraviolet lamp used when irradiating ultraviolet rays include a discharge lamp method, a flash method, a laser method, and an electrodeless lamp method. When using a high-pressure mercury lamp that is a discharge lamp method, the conditions for ultraviolet illuminance are preferably 100 to 3,000 mW / cm ² , more preferably 200 to 2,000 mW / cm ² , and more preferably 300 to 1,500 mW / cm ² UV irradiation is preferred. In accumulated light amount of ultraviolet rays is preferably 100 ~ 3,000mJ / cm ^2, more preferably 200 ~ 2,000mJ / cm ^2, and then is irradiated with ultraviolet rays under good conditions 300 ~ 1,500mJ / cm ² is preferred. Here, the illuminance of ultraviolet rays refers to the intensity of irradiation per unit area, which varies with the output power of the lamp, the luminous spectral efficiency, the diameter of the light bulb, the design of the reflector, and the distance from the light source of the object to be irradiated. However, the illumination does not change with the speed of transportation. The cumulative amount of ultraviolet light refers to the irradiation energy per unit area, that is, the total amount of photons reaching the surface. The accumulated light amount is inversely proportional to the irradiation speed under the light source, and proportional to the number of irradiations and the number of lamps.

[Example]

Next, an explanation will be given based on the examples, but the present invention is not necessarily limited to these.

[Carbamate (meth) acrylate A]

[Synthesis of urethane (meth) acrylate A1]

100 parts by mass of toluene, 50 parts by mass of 2,6-diisocyanate methyl hexanoate (LDI manufactured by Kyowa Fermentation Kirin Co., Ltd.) and 119 parts by mass of polycarbonate diol (PLACCEL manufactured by DAICEL Chemical Industry Co., Ltd.) CD-210HL), and heated to 40 ° C for 8 hours. Thereafter, 28 parts by mass of 2-hydroxyethyl acrylate (LIGHTESTER HOA, manufactured by Kyoeisha Chemical Co., Ltd.), 5 parts by mass of dipentaerythritol hexaacrylate (M-400, manufactured by Toa Synthesis Co., Ltd.), 0.02 After mass parts of hydroquinone monomethyl ether was maintained at 70 ° C. for 30 minutes, 0.02 parts by mass of dibutyl lauryl tin was added and maintained at 80 ° C. for 6 hours. Then, 97 parts by mass of toluene was finally added to obtain a urethane acrylate A1 having a solid content concentration of 50% by mass.

[Synthesis of carbamate (meth) acrylate A2]

100 parts by mass of toluene, 50 parts by mass of 2,6-diisocyanate methyl hexanoate (Kyowa Fermentation Kirin Co., Ltd. LDI) and 150 parts by mass of polycarbonate diol (DAICEL Chemical Industry Co., Ltd. PLACCEL CD-220), mixed and heated to 40 ° C for 8 hours. Thereafter, 28 parts by mass of 2-hydroxyethyl acrylate (LIGHTESTER HOA, manufactured by Kyoeisha Chemical Co., Ltd.), 5 parts by mass of dipentaerythritol hexaacrylate (M-400, manufactured by Toa Synthesis Co., Ltd.), and 0.02 were added. Mass parts of hydroquinone monomethyl ether, and after maintaining at 70 ° C for 30 minutes, 0.02 mass parts of dibutyl ether was added Cinnamon, held at 80 ° C for 6 hours. Then, 97 parts by mass of toluene was finally added to obtain a urethane acrylate A2 having a solid content concentration of 50% by mass.

[Synthesis of urethane (meth) acrylate A3]

100 parts by mass of toluene, 50 parts by mass of 2,6-diisocyanatomethylhexanoate (LDI manufactured by Kyowa Fermentation Kirin Co., Ltd.) and 110 parts by mass of polycarbonate diol (DURANOL T5651, manufactured by Asahi Kasei Co., Ltd.) Mix and heat to 40 ° C for 8 hours. Thereafter, 28 parts by mass of 2-hydroxyethyl acrylate (LIGHTESTER HOA, manufactured by Kyoeisha Chemical Co., Ltd.), 5 parts by mass of dipentaerythritol hexaacrylate (M-400, manufactured by Toa Synthesis Co., Ltd.), 0.02 After mass parts of hydroquinone monomethyl ether was maintained at 70 ° C. for 30 minutes, 0.02 parts by mass of dibutyl lauryl tin was added and maintained at 80 ° C. for 6 hours. Then, 97 parts by mass of toluene was finally added to obtain a urethane acrylate A3 having a solid content concentration of 50% by mass.

[Synthesis of urethane (meth) acrylate A4]

100 parts by mass of toluene, 50 parts by mass of 2,6-diisocyanatomethylhexanoate (LDI manufactured by Kyowa Fermentation Kirin Co., Ltd.) and 60 parts by mass of polycarbonate diol (DURANOL T5650E, manufactured by Asahi Kasei Co., Ltd.) Mix and heat to 40 ° C for 8 hours. Thereafter, 28 parts by mass of 2-hydroxyethyl acrylate (LIGHTESTER HOA, manufactured by Kyoeisha Chemical Co., Ltd.), 5 parts by mass of dipentaerythritol hexaacrylate (M-400, manufactured by Toa Synthesis Co., Ltd.), 0.02 After mass parts of hydroquinone monomethyl ether was maintained at 70 ° C. for 30 minutes, 0.02 parts by mass of dibutyl lauryl tin was added and maintained at 80 ° C. for 6 hours. Then, 97 parts by mass of toluene was finally added to obtain a urethane acrylate A4 having a solid content concentration of 50% by mass.

[Carbamate (meth) acrylate B]

[Synthesis of carbamate (meth) acrylate B1]

100 parts by mass of toluene, 50 parts by mass of 2,6-diisocyanatomethylhexanoate (LDI manufactured by Kyowa Fermentation Kirin Co., Ltd.) and 110 parts by mass of polycarbonate diol (PLACCEL manufactured by DAICEL Chemical Industry Co., Ltd.) CD-210HL) and 8 parts by mass of polydimethylsiloxane (X-22-160AS manufactured by Shin-Etsu Chemical Industry Co., Ltd.) were mixed and heated to 40 ° C. for 8 hours. Thereafter, 28 parts by mass of 2-hydroxyethyl acrylate (LIGHTESTER HOA, manufactured by Kyoeisha Chemical Co., Ltd.), 5 parts by mass of dipentaerythritol hexaacrylate (M-400, manufactured by Toa Synthesis Co., Ltd.), 0.02 After mass parts of hydroquinone monomethyl ether was maintained at 70 ° C. for 30 minutes, 0.02 parts by mass of dibutyl lauryl tin was added and maintained at 80 ° C. for 6 hours. Then, 97 parts by mass of toluene was finally added to obtain a urethane acrylate B1 having a solid content concentration of 50% by mass.

[Urethane (meth) acrylate C]

[Synthesis of carbamate (meth) acrylate C1]

50 parts by mass of toluene, 50 parts by mass of hexamethylene diisocyanate modified isocyanurate (TAKENATE D-170N manufactured by Mitsui Chemicals Co., Ltd.), and 76 parts by mass of polycaprolactone modified acrylic hydroxyethyl Esters (PLACCEL FA5 manufactured by DAICEL Chemical Industry Co., Ltd.), 0.02 parts by mass of dibutyl lauryl tin, and 0.02 parts by mass of hydroquinone monomethyl ether were mixed and kept at 70 ° C. for 5 hours. Thereafter, 79 parts by mass of toluene was added to obtain a urethane acrylate C1 having a solid content concentration of 50% by mass.

[Synthesis of carbamate (meth) acrylate C2]

50 parts by mass of hexamethylene diisocyanate modified isocyanate (TAKENATE D-170N manufactured by Mitsui Chemicals Co., Ltd .; isocyanate group content: 20.9% by mass), 53 parts by mass of polyethylene glycol-1 Acrylate (BLEMMER AE-150, manufactured by Nippon Oil Co., Ltd .; Hydroxyl value: 264 (mgKOH / g)), 0.02 parts by mass of dibutyl lauryl tin and 0.02 parts by mass of hydroquinone monomethyl ether. Thereafter, the reaction was carried out by keeping the temperature at 70 ° C for 5 hours. After completion of the reaction, 102 parts by mass of methyl ethyl ketone (hereinafter referred to as MEK) was added to the reaction solution to obtain a urethane acrylate C2 having a solid content concentration of 50% by mass.

[Synthesis of carbamate (meth) acrylate C3]

50 parts by mass of toluene, 67 parts by mass of H6XDI NURATE (D-127N manufactured by Mitsui Chemicals Co., Ltd .; NCO content of 13.5% by mass) and 76 parts by mass of polycaprolactone modified hydroxyethyl acrylate (manufactured by DAICEL Chemical Industry Co., Ltd.) PLACCEL FA5), 0.02 parts by mass of dibutyl lauryl tin, and 0.02 parts by mass of hydroquinone monomethyl ether were mixed and kept at 70 ° C for 5 hours. Thereafter, 79 parts by mass of toluene was added to obtain a urethane acrylate C3 having a solid content concentration of 50% by mass.

[Siloxane compound]

[Siloxanes Compound 1]

As the silicone compound 1, a silicon diacrylate compound (EBECRYL350 DAICEL. CYTECH Co., Ltd.) was used.

[Siloxanes Compound 2]

As the siloxane compound 2, a silicon hexaacrylate compound (EBECRYL1360 DAICEL. CYTECH Co., Ltd.) was used.

[Synthesis of polysiloxane (a)]

A 500-ml flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen introduction tube was charged with 106 parts by mass of ethanol, 320 parts by mass of tetraethoxysilane, 21 parts by mass of deionized water, and 1 part by mass of 1% by mass hydrochloric acid. After being kept at 85 ° C for 2 hours, ethanol was recovered while heating up, and kept at 180 ° C for 3 hours. Thereafter, it was cooled to obtain a thick polysiloxane (a).

[Polydimethylsiloxane-based block copolymer (a)]

Using the same device as the synthesis of polysiloxane (a), 50 parts by mass of toluene, 50 parts by mass of methyl isobutyl ketone, and 20 parts by mass of polydimethylsiloxane-based polymer polymerization initiator (WPS-0501, manufactured by Wako Pure Chemical Industries, Ltd.), 30 parts by mass of methyl methacrylate, 26 parts by mass of butyl methacrylate, 23 parts by mass of 2-hydroxyethyl methacrylate, 1 part by mass of methacrylic acid, and 0.5 part by mass of 1-thioglycerol was reacted at 80 ° C for 8 hours to obtain a polydimethylsiloxane-based block copolymer (a). The proportion of the block copolymer (a) in the obtained solution was 50% by mass in a 100% by mass solution.

[Polydimethylsiloxane-based graft copolymer (b)]

Using an apparatus used for the synthesis of polysiloxane (a), 50 parts by mass of toluene and 50 parts by mass of isobutyl acetate were charged, and the temperature was raised to 110 ° C. In addition, 20 parts by mass of methyl methacrylate, 20 parts by mass of butyl methacrylate, 32 parts by mass of caprolactone methacrylate (PLACCEL FM-5 manufactured by DAICEL Chemical Industry Co., Ltd.), and 23 parts by mass of methacrylic acid 2-hydroxyethyl ester, 10 parts by mass of polysiloxane (a), 20 parts by mass of one-sided terminal methacrylic acid modified polydimethylsiloxane (X-22-174DX, manufactured by Toa Synthetic Chemical Industry Co., Ltd.) And 1 part by mass of methacrylic acid, 2 parts by mass of 1,1-azobiscyclohexane-1- Carbonitrile is mixed. This mixed monomer was dropped onto the above-mentioned mixed liquid of toluene and butyl acetate over 2 hours. Then, it was made to react at 110 degreeC for 8 hours, and the polydimethylsiloxane graft copolymer (b) which has a hydroxyl group and has a solid content concentration of 50 mass% was obtained. The proportion of the graft copolymer (b) in the obtained solution was 50% by mass in a 100% by mass solution.

[Acrylic polyol]

[Acrylic polyol 1]

As the acrylic polyol 1, a hydroxyl group-containing acrylic polyol was used ("TAKELAC" (registered trademark) UA-702 Mitsui Chemicals Co., Ltd., solid content concentration: 50% by mass, hydroxyl group value: 50 mgKOH / g).

[Acrylic polyol 2]

As the acrylic polyol 2, an acrylic polyol containing a hydroxyl group ("ACRYDIC" (registered trademark) A-823 DIC Corporation, with a solid content concentration of 50% by mass and a hydroxyl group valence of 30 mgKOH / g) was used.

[Isocyanate compound]

[Isocyanate compound 1]

As the isocyanate compound 1, methylenephenyl diisocyanate ("CORONATE" (registered trademark) L Japan Polyurethane Industrial Co., Ltd .; solid content concentration 75% by mass and NCO content 13.5% by mass) was used.

As the isocyanate compound, methylenediphenyl diisocyanate ("CORONATE" (registered trademark) CORONATE L Japan Polyurethane Industrial Co., Ltd .; solid content concentration 75% by mass NCO content 13.5% by mass)) was used.

[Multifunctional acrylate]

[Multifunctional acrylate 1]

As the polyfunctional acrylate 1, a urethane acrylate oligomer ("SHIKOH" (registered trademark) UV-3310B manufactured by Nippon Synthetic Chemical Industry Co., Ltd .; solid content concentration 100% by mass) was used.

[Multifunctional acrylate 2]

As the polyfunctional acrylate 2, a urethane acrylate oligomer ("SHIKOH" (registered trademark) UV-1700B manufactured by Nippon Synthetic Chemical Industry Co., Ltd .; solid content concentration 100% by mass) was used.

[Multifunctional acrylate 3]

As the polyfunctional acrylate 3, a urethane acrylate oligomer ("SHIKOH" (registered trademark) UV-2750B manufactured by Nippon Synthetic Chemical Industry Co., Ltd .; solid content concentration: 100% by mass) was used.

[Acrylic polymer]

[Synthesis of acrylic polymer 1]

24 parts by mass of dilauryl peroxide (PEROYL L; manufactured by Nippon Oil Co., Ltd.) was added to 495 parts by mass of methyl ethyl ketone, heated at 70 ° C for 30 minutes to dissolve, and mixed with 50 drops by dripping for 4 hours. Parts by mass of methacrylic acid, 90 parts by mass of butyl acrylate, 100 parts by mass of methyl methacrylate, and 2.4 parts by mass of 4-methyl-2,4-diphenylpentene-1 (NOFMER MSD; Nippon Oil Co., Ltd. ) Solution was stirred and polymerized. Then, it stirred at 80 degreeC for 2 hours, and obtained the methyl ethyl ketone solution (weight average molecular weight 6,000) of the acrylic polymer 1 containing the solid content concentration of the hydrophilic functional group of 35 mass%.

[Blend of coating composition A]

[Coating composition A1]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A1 having a solid content concentration of 30% by mass.

[Coating composition A2]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A2 having a solid content concentration of 30% by mass.

[Coating composition A3]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A3 having a solid content concentration of 30% by mass.

[Coating composition A4]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A4 having a solid content concentration of 30% by mass.

[Coating composition A5]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A5 having a solid content concentration of 30% by mass.

[Coating composition A6]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A6 having a solid content concentration of 30% by mass.

[Blend of coating composition B]

[Coating composition B1]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B1 having a solid content concentration of 30% by mass.

[Coating composition B2]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B2 having a solid content concentration of 30% by mass.

[Blend of coating composition C]

[Coating composition C1]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition C1 having a solid content concentration of 50% by mass.

[Coating composition C2]

The following materials were mixed and diluted with methyl ethyl ketone to obtain Coating composition C2 having a solid content concentration of 50% by mass.

[Coating composition C3]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition C3 having a solid content concentration of 50% by mass.

[Coating composition C4]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition C4 having a solid content concentration of 50% by mass.

[Blend of coating composition D]

[Coating composition D1]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition D1 having a solid content concentration of 40% by mass.

． 15 parts by mass of polycaprolactone triol

[Coating composition D2]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition D2 having a solid content concentration of 40% by mass.

[Blend of coating composition for intermediate layer]

[Coating composition X1]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition X1 having a solid content concentration of 20% by mass.

[Coating composition X2]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition X2 having a solid content concentration of 20% by mass.

[Coating composition X3]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition X3 having a solid content concentration of 20% by mass.

[Coating composition X4]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition X4 having a solid content concentration of 20% by mass.

[Coating composition X5]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition X5 having a solid content concentration of 20% by mass.

("IRGACURE" (registered trademark) 184 BASF JAPAN Co., Ltd.).

[Coating composition X6]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition X6 having a solid content concentration of 20% by mass.

[Support substrate]

[Support substrate A1]

As the supporting substrate A1, "COSMOSHINE" (registered trademark) A4300 (125 μm in thickness; manufactured by Toyobo Co., Ltd.) was used.

[Support substrate A2]

As the supporting substrate A2, "Panlite" (registered trademark) PC-2151 (125 μm in thickness; manufactured by Teijin Kasei Co., Ltd.) was used.

[Supporting substrate B1]

As the supporting substrate B1, "Lumirror" (registered trademark) U48 (125 μm in thickness; manufactured by TORAY Co., Ltd.) was used.

[Swelling Index of Supporting Substrate]

The swelling index of the supporting substrate is calculated by the following method. First, the haze value h ₁ (%) of the supporting substrate was measured. Next, methyl ethyl ketone was coated on a supporting substrate with a bar coater (# 10), and left at a temperature of 40 ° C for 1 minute to dry the methyl ethyl ketone. Thereafter, the haze value h ₂ (%) of the support substrate after drying was measured. Using these two values, the swelling index was calculated from the following formula. The measurement was performed three times for each sample change site, and the average value was used.

Swelling index: h = | h ₂ -h ₁ |

In addition, the measurement of the haze value is based on JIS K 7136 (2000), and a haze meter manufactured by Nippon Denshoku Industries Co., Ltd. is used to transmit light from the side on which the methyl ethyl ketone is coated on the supporting substrate. Measurements were performed on the device. Table 1 summarizes the evaluation results of the supporting substrates.

[Manufacturing method of laminated film]

[Production of laminated film 1]

On the supporting substrate, the aforementioned coating composition A (A1 to A6), coating composition B (B1 to B2), and coating composition C (C1 to C4) were applied by a continuous coating device using a slit die coater. The thickness of the surface layer after the application was dried while adjusting the discharge flow rate from the slit was a predetermined film thickness. The conditions of the drying air blown to the liquid film during the period from coating to drying and curing are as follows.

[Drying step]

Supply air temperature and humidity: temperature: 80 ° C, relative humidity: 1% or less

Wind speed: coating surface side: 5m / s, opposite coating surface side: 5m / s

Wind direction: coating surface side: parallel to the substrate surface, opposite coating surface side: perpendicular to the substrate surface

Detention time: 2 minutes

[Hardening step]

Irradiation output power: 400W / cm ²

Cumulative light quantity: 120mJ / cm ²

Oxygen concentration: 0.1% by volume.

[Production of laminated film 2]

On the supporting substrate, the coating composition D (D1 to D2) is applied by a continuous coating device using a slit die coater to adjust the discharge flow rate from the slit to form a dried surface layer having a specified thickness. Of film thickness. The conditions of the drying air blown to the liquid film during the period from coating to drying and curing are as follows.

[Drying step]

Supply air temperature and humidity: temperature: 80 ° C, relative humidity: 1% or less

Wind speed: coating surface side: 5m / s, opposite coating surface side: 5m / s

Wind direction: coating surface side: parallel to the substrate surface, opposite coating surface side: perpendicular to the substrate surface

Detention time: 1 minute

[Hardening step]

Supply air temperature and humidity: temperature: 160 ℃, relative humidity: 1% or less

Wind speed: coating surface side: 10m / s, opposite coating surface side: 10m / s

Wind direction: coating surface side: perpendicular to the substrate surface, opposite coating surface side: perpendicular to the substrate surface

Detention time: 2 minutes

In addition, the aforementioned wind speed, temperature, and humidity are measured values using a heating wire type anemometer (Anemomaster wind speed-anemometer MODEL 6034 manufactured by KANOMAX Corporation, Japan).

The laminated films of Examples 1 to 13 and Comparative Examples 1 to 6 were prepared by the above methods. The production methods of the above-mentioned laminated films corresponding to the respective examples and comparative examples, and the film thicknesses of the respective layers are described in Tables 2 to 4.

[Production of laminated film 3]

The coating composition for the intermediate layer was applied to a support substrate using a continuous coating device of a slit die coater, and the thickness of the surface layer after coating was adjusted to a predetermined film thickness by adjusting the discharge flow rate from the slit. The drying step and the hardening step are performed under the following conditions to form an intermediate layer on the supporting substrate.

[Drying step]

Supply air temperature and humidity: Temperature: 80 ℃

Wind speed: coating surface side: 5m / s, opposite coating surface side: 5m / s

Wind direction: coating surface side: parallel to the substrate surface, opposite coating surface side: perpendicular to the substrate surface

Detention time: 2 minutes.

[Hardening step]

Cumulative light quantity: 120mJ / cm ²

Oxygen concentration: atmospheric environment

Furthermore, using the same device, on the intermediate layer obtained above, the coating composition was applied to adjust the discharge flow rate from the slit so that the thickness of the surface layer after drying was a predetermined film thickness, and then the drying step was performed under the following conditions And a curing step to obtain a laminated film.

[Drying step]

Supply air temperature and humidity: Temperature: 80 ℃

Wind speed: coating surface side: 5m / s, opposite coating surface side: 5m / s

Wind direction: coating surface side: parallel to the substrate surface, opposite coating surface side: perpendicular to the substrate surface

Detention time: 2 minutes

[Hardening step]

Cumulative light quantity: 120mJ / cm ²

Oxygen concentration: 200 ppm or less.

[Production of laminated film 4]

The coating composition for the intermediate layer was applied to a support substrate using a continuous coating device of a slit die coater, and the thickness of the surface layer after coating was adjusted to a predetermined film thickness by adjusting the discharge flow rate from the slit. The drying step and the hardening step are performed under the following conditions to form an intermediate layer on the supporting substrate.

[Drying step]

Supply air temperature and humidity: Temperature: 80 ℃

Wind speed: coating surface side: 5m / s, opposite coating surface side: 5m / s

Wind direction: coating surface side: parallel to the substrate surface, opposite coating surface side: perpendicular to the substrate surface

Detention time: 2 minutes

Furthermore, using the same device, on the intermediate layer obtained above, the coating composition was applied to adjust the discharge flow rate from the slit so that the thickness of the surface layer after drying was a predetermined film thickness, and then the drying step was performed under the following conditions. And a curing step to obtain a laminated film.

[Drying step]

Supply air temperature and humidity: Temperature: 80 ℃

Wind speed: coating surface side: 5m / s, opposite coating surface side: 5m / s

Wind direction: coating surface side: parallel to the substrate surface, opposite coating surface side: perpendicular to the substrate surface

Detention time: 2 minutes.

[Hardening step]

Cumulative light quantity: 120mJ / cm ²

Oxygen concentration: 200 ppm or less.

According to the above method, the laminated films of Examples 14 to 22 were prepared. The production methods of the above-mentioned laminated films corresponding to the respective examples and comparative examples, and the film thicknesses of the respective layers are described in Tables 2 to 4.

[Evaluation of laminated film]

The produced laminated film was subjected to performance evaluation shown below, and the obtained results are shown in Tables 3 and 4. Unless otherwise specified, the measurement was performed three times in each of the examples / comparative examples, and the average value was used.

[Relative storage modulus of surface layer]

Based on a rigid pendulum free damping vibration method (which is a rigid pendulum test method), a rigid pendulum type physical property testing machine RPT-3000 manufactured by A & D Co., Ltd. was used to determine the relative storage elastic modulus of the surface layer. The testing machine was adjusted to 25 ° C in advance, and after the sample and the pendulum were installed, the temperature was increased to 150 ° C at a rate of 10 ° C / minute for measurement. The measurement was performed 5 times each, and the average value was evaluated. In addition, the pendulum uses the following.

Used blade: Knife blade (RBE-160 made by A & D Co., Ltd.)

Mass of pendulum / inertial energy rate: 15g / 640g. cm (A & D Corporation FRB-100)

The relative storage elastic modulus at a measurement temperature of 25 ° C. was G ′ ₂₅ , and the relative storage elastic modulus at a measurement temperature of 100 ° C. was G ′ ₁₀₀ .

[Crack Elongation of Surface Layer]

The laminated film was cut into a width of 10 mm x a length of 200 mm, and was clamped with a chuck along the length direction. The film was stretched at a stretching speed of 100 mm / min using an Instron type tensile tester (Instron's ultra-precision material tester MODEL 5848). . The measurement temperature was performed at 150 ° C. When stretching, first observe the sample during stretching, and stop it if cracks (cracks) occur visually (elongation at the time of stopping is adjusted to an integer of 5). The sample to be measured next is a sample in which the elongation at the time of stopping is sequentially reduced, and the tensile elongation is continuously reduced by 5%, and the elongation at which no cracks are finally visually observed is performed.

Cut out the film cross section of the cracked portion of the sample, observe the surface layer at a magnification of 30 mm or more on the observation screen of the transmission electron microscope, and observe the surface layer with a thickness of 50% or more of the average thickness of the surface layer. The occurrence of cracks is regarded as "cracked" (the surface layer is damaged), and the elongation value of the specimen with the lowest elongation among the specimens regarded as "cracked" is the fracture elongation. Thereafter, the same measurement was performed a total of three times, and the average value of their fracture elongation was used as the fracture elongation of the surface layer.

[Maximum displacement in the thickness direction of the surface layer, and residual displacement]

Apply 1g of Dow to a smooth metal plate (mold steel: SKD-11) "High Vacuum Grease" manufactured by Corning Toray Co., Ltd. Adheres the support substrate side of the laminated film to the part coated with the high vacuum grease toward it, wrap the filter paper on the surface and use a hand press to prevent the air from getting stuck Press. From the surface layer side of the sample obtained in this way, a stress-displacement curve was obtained by measuring under a load-unloading test method using a regular triangular cone under the following conditions (see Fig. 1).

From the line graph, the displacement amount (maximum displacement amount) in the thickness direction after the load was applied and before unloading, and the displacement amount (residual displacement amount) in the thickness direction at the end of the test were obtained.

Device: Dynamic Ultra-Miniature Hardness Tester "DUH-201" (manufactured by Shimadzu Corporation)

Indenter used: Diamond triangular pyramid indenter (angle between edges 115 °)

Measurement mode: 2 (load-unload test method)

Maximum load: 0.5mN

Hold time at maximum load: 10 seconds

Load speed and unload speed: 0.1422mN / s.

[Measurement of glass transition temperature of intermediate layer]

A. Confirmation of laminated film cross section

The laminated film was cut out with a cutter, embedded with an epoxy resin for an electron microscope (Quetol 812, manufactured by Nisshin EM Co., Ltd.), and the epoxy resin was hardened in an oven at 60 ° C. for 48 hours. (Ultracut S manufactured by Leica) was made into ultra-thin sections with a thickness of about 100 nm.

The produced ultra-thin sections were mounted on a 100-mesh Cu grid manufactured by Asahi Corporation and a transmission electron microscope manufactured by Hitachi was used. H-7100FA was subjected to TEM observation at an acceleration voltage of 100 kV, and the cross-section of the laminated film was observed to confirm the surface layer, the intermediate layer, and the space supporting the substrate.

B. Measurement using an ultra-micro hardness tester

Based on the above, the ultra-thin section was used as a sample, and the module mapping images of the surface layer, the intermediate layer, and the supporting substrate were obtained using an ultra-micro hardness tester (Tribo Indenter manufactured by Hysitron), and the storage elastic modulus and loss elastic modulus were calculated , And the loss tangent (tanδ) is obtained from the ratio of the storage elastic modulus to the loss elastic modulus, and the peak temperature of the obtained loss tangent (tanδ) is used as the glass transition temperature (Tg).

The measurement conditions are shown below.

Measuring device: Tribo Indenter by Hysitron

Indenter: Diamond Cubecorner (curvature radius 50nm)

Measurement field of view: about 30mm square

Measuring cycle number: 10Hz

Measurement environment: -20 ℃ ~ 120 ℃. In the atmosphere

Contact load: 0.3 μN.

[Self-healing properties of the surface layer]

After standing at a temperature of 23 ° C for 12 hours, the surface of the surface layer was scraped horizontally 5 times under the same load on a brass wire brush (manufactured by TRUSCO) under the same environment, and then left for 5 minutes. The abrasion recovery status was determined visually according to the following criteria. The test was performed 3 times, and the average value (rounded down to the decimal point) was taken as the test result, and 4 or more points were passed.

10 points: No abrasion under 1kg load

7 points: Although abrasion remains under a load of 1kg, there is no abrasion under 700g

4 points: Although abrasion remained under a load of 700g, no abrasion remained under 500g

1 point: Abrasions remain under a load of 500 g.

[Design of surface layer]

Regarding the recovery state of the scratch when the surface of the surface layer was scraped horizontally 5 times under a load of 500g on a brass wire brush (manufactured by TRUSCO) in the same environment after being left at a temperature of 23 ° C for 12 hours, the following conditions were applied. The reference is judged visually. The test was performed 3 times, and the average value (rounded down to the decimal point) was taken as the test result, and 4 or more points were passed.

10 minutes: The time required for the full recovery of the abrasion on the surface is less than 3 seconds.

7 points: The time required for the full recovery of the abrasion on the surface is longer than 3 seconds and less than 10 seconds.

4 points: The time required for the surface abrasion to fully recover is longer than 10 seconds and less than 30 seconds.

1 point: Other (the time required for the full recovery of the surface abrasion is longer than 30 seconds, there is an irrecoverable abrasion, or the abrasion is not marked, etc.).

[High-speed deformation resistance of the surface layer]

Regarding the surface of the surface layer after being left at a temperature of 23 ° C for 12 hours under the same environment, a brass wire brush (manufactured by Trusco) was placed under the weight below 5 times from a height of 10 cm, The state is judged visually based on the following criteria. The test was performed 3 times, and the average value (rounded down to the decimal point) was taken as the test result, and 4 or more points were passed.

10 points: No scratches or marks remain under the weight of 1kg.

7 points: Although abrasions or marks remain under the weight of 1kg, there is no residue under 700g Stay bruised.

4 points: Although abrasions or marks remained under the weight of 700g, no abrasions remained under 500g.

1 point: Abrasions remain under a weight of 500 g.

[Formability of surface layer]

The formability of the surface layer is determined based on the fracture elongation of the surface layer according to the following criteria, and a score of 4 or more is acceptable.

10 points: The fracture elongation of the surface layer is 100% or more.

7 points: The fracture elongation of the surface layer is 70% or more and less than 100%.

4 points: The fracture elongation of the surface layer is 50% or more and less than 70%.

1 point: The fracture elongation of the surface layer is less than 50%.

[Peeling of surface layer]

Each value and the value required for evaluation are obtained by the following tensile test method.

As a tensile test method and a treatment before measurement of the amount of chloroform dissolved, only the surface layer was peeled from the laminated film according to the following method to prepare a test sample.

First, the laminated film was immersed in ethanol and allowed to stand at 25 ° C for 10 minutes. Thereafter, the surface layer of the laminated film was peeled off from the supporting substrate to prepare a measurement sample.

[Evaluation of breaking elongation, elastic recovery rate, yield point of stress-strain curve, fracture energy per unit volume]

Each value and the value required for evaluation are obtained by the following tensile test method. In addition, a sample is taken by peeling the aforementioned surface layer.

[Tensile test method]

Cut the surface layer along the length and width directions to a length of 150mm × width A 10 mm rectangle was made into a test piece. Using a tensile tester (Tensilon UCT-100 manufactured by Orientec), set the initial tension chuck distance to 50mm, set a specific stretching speed, and install the test piece in a thermostatic bath set to a specific measurement temperature in advance. The tensile test was performed after a 90 second warm-up. Since the stretching speed and measurement temperature differ depending on the evaluation items, they are described for each item.

The load b (N) applied to the sample when the distance between the chucks was a (mm) was read, and the strain amount x (%) and the stress y (MPa) were calculated from the following formulas. However, the thickness of the sample before the test is set to k (mm).

Strain variable: x = ((a-50) / 50) × 100

Stress: y = b / (k × 10).

[Breaking elongation]

In the tensile test method with a tensile speed of 50 mm / min and a measurement temperature of 25 ° C., the elongation at break of the test piece was taken as the elongation at break. The measurement was performed five times for each sample, and the average value was evaluated.

[Flexible recovery rate]

In a tensile test method with a tensile speed of 50 mm / min and a measurement temperature of 25 ° C., the sample was stretched to a strain amount of 150%, and then the tensile load on the sample was released. (This is the tensile test method at 150% deformation)

The marked distance was measured before the measurement, and Lmm was set as the initial sample length, and the elastic recovery rate z% was calculated from the following formula.

Elastic recovery rate: z = (1- (L-50) / 100) × 100

In addition, under the above-mentioned measurement conditions, since the specimen having a breaking elongation of less than 150% was broken, the elastic recovery rate could not be measured.

[Evaluation of yield point of stress-strain curve]

A stress-strain curve was obtained by a tensile test method with a tensile speed of 50 mm / min and a measurement temperature of 25 ° C. The measurement was performed five times for each sample, and the average value was evaluated.

In the obtained stress-strain curve, let the stress under a certain strain x _a be y _a and the stress under _a certain strain x _b be y _b . For any x _a and x _b, the following conditional expressions are satisfied: , It is deemed that there is no yield point. On the other hand, if the following conditional expression is not satisfied, it is considered that there is a yield point.

Conditional expression: y _a ≦ y _b

However, x _a ≦ x _b , x _{a is} greater than 0%, and x _{b is} less than the breaking elongation.

[Fracture energy per unit volume]

A stress-strain curve was obtained by a tensile test method with a tensile speed of 50 mm / min and a measurement temperature of 25 ° C. The measurement was performed five times for each sample, and the average value was evaluated.

In the obtained stress-strain curve, the integrated area drawn by the x-axis and the stress-strain curve is calculated to obtain the fracture energy per unit volume.

[Dissolved amount of chloroform]

Each value and the value required for evaluation are obtained by the following tensile test method.

The sample obtained by peeling the aforementioned surface layer was cut into a length of 5 cm × 5 cm, and its mass g _{1 was} measured. Next, the sample was immersed in chloroform and left to stand at 25 ° C for 60 minutes. The sample was taken out from chloroform, and the wiping operation was performed under a load of 50 g using a gauze, and the mass g ₂ of the sample after the wiping was measured. Using these two values, the amount of chloroform dissolved g (mass%) was calculated from the following formula.

The amount of chloroform dissolved: g = (g ₁ -g ₂ ) / g ₁

Tables 3 and 4 summarize the evaluation results of the laminated films finally obtained.

[Industrial availability]

The laminated film of the present invention is particularly suitable for applications that require high designability in applications where it is formed into various types of molded bodies by utilizing the advantages of formability, self-healing, designability, and high-speed deformation resistance. And want to cover the use of abrasions. Specifically, it can be suitably used in plastic products such as glasses, sunglasses, cosmetic cases, food containers, housings of smart phones, touch panels, keyboards, televisions, air-conditioners and other electrical appliances, buildings, and meters. Panels, car navigation-touch panels, car mirrors and other vehicle interior items, as well as various surfaces of printed matter.

Claims (6)

A laminated film is a laminated film having a surface layer on at least one side of a supporting substrate, wherein the supporting substrate is composed of one or more resins selected from a thermoplastic resin and a thermosetting resin, and the surface layer system The following condition 9 is satisfied. The laminated film satisfies the following conditions 1 to 3, and satisfies one or more conditions selected from the following condition 6, condition 11 and condition 12: condition 9: the resin contained in the surface layer includes the following (1) to (3): (1) polycarbonate segment; (2) urethane bond; (3) polysiloxane segment and / or polydimethylsiloxane chain of chemical formula 3 segment; R ₂ and R ₃ are each of OH and an alkyl group having 1 to 8 carbon atoms; the polysiloxane segment has at least one OH and alkyl group; n ₂ is an integer of 100 to 300; 1: Under the conditions of a maximum load of 0.5 mN and a retention time of 10 seconds, the maximum displacement in the thickness direction of the surface layer in the load-unload test method using a micro hardness tester is 1.50 μm or more, and the thickness direction of the surface layer The residual displacement is 1.30 μm or less; Condition 2: The relative storage elastic modulus of the surface layer at 100 ° C in the rigid pendulum test method is higher than the relative storage elastic modulus of the surface layer at 25 ° C; Condition 3: The elongation at break of the surface layer at 150 ° C in a tensile test method is 50% or more; Condition 6: The swelling index of the support substrate is 0.01 or more; Condition 11: further has an intermediate layer, intermediate The layer and surface layer are connected to the supporting substrate in this order, and the glass transition temperature of the intermediate layer is 60 ° C or higher and 130 ° C or lower; Condition 12: further having an intermediate layer, the intermediate layer and the surface layer are connected in this order On a support substrate, and the thickness of the intermediate layer is 0.1 μm or more and 5 μm or less ; Wherein the intermediate layer comprises at least one resin selected from thermosetting resin and an ultraviolet curable resin. For example, the laminated film of claim 1, wherein the laminated film satisfies the following conditions 4 and 5: Condition 4: The tensile elongation at break of the surface layer at 25 ° C is more than 150%; Condition 5: In the tensile test method at a deformation amount of 150%, the elastic recovery rate of the surface layer at 25 ° C. is 70% or more. For example, the laminated film of claim 1 or 2, wherein the laminated film satisfies the following conditions 7 and 8: condition 7: there is no yield point on the stress-strain curve of the surface layer in the tensile test method Condition 8: The breaking energy per unit volume of the surface layer in the tensile test method is 500 MPa or more. For example, the laminated film of claim 1 or 2, wherein the laminated film satisfies the following condition 10: Condition 10: the surface layer has a chloroform dissolved amount of 3% by mass or more and 20% by mass or less. For example, the laminated film of claim 1 or 2, wherein the laminated film satisfies the following condition 13: Condition 13: The surface layer and / or the intermediate layer are sequentially coated on a supporting substrate by two or more coating compositions , And formed by drying and hardening. For example, the laminated film of claim 1 or 2, wherein the laminated film satisfies the following condition 14: Condition 14: The surface layer and / or the intermediate layer are coated on a supporting substrate by applying two or more coating compositions simultaneously. , And formed by drying and hardening.